WO2018166096A1 - 一种有机发光器件及其制备方法 - Google Patents

一种有机发光器件及其制备方法 Download PDF

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WO2018166096A1
WO2018166096A1 PCT/CN2017/089607 CN2017089607W WO2018166096A1 WO 2018166096 A1 WO2018166096 A1 WO 2018166096A1 CN 2017089607 W CN2017089607 W CN 2017089607W WO 2018166096 A1 WO2018166096 A1 WO 2018166096A1
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organic light
triphenylamine
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潘彪
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Wuhan China Star Optoelectronics Technology Co Ltd
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Definitions

  • the invention belongs to the field of flexible display technologies, and in particular to the preparation of an organic light emitting device.
  • the maximum external quantum efficiency (EQE) of the green OLED is 8%, which breaks the theoretical limit of the electroluminescent device, and people pay great attention to the phosphorescent material. . Since then, electrophosphorescent materials and phosphorescent devices have been the focus of OLED research.
  • electrophosphorescent devices Due to the long lifetime of triplet excitons, in order to suppress the quenching process of triplet-triplet excitons in devices at high concentrations, electrophosphorescent devices generally adopt host-guest-doped device structures, ie, phosphorescent host materials.
  • a certain percentage of the phosphorescent guest material is doped as a light-emitting layer.
  • the luminescence mechanism of the device is the energy transfer mode of the host object or the direct capture mode of the carrier on the object. The former way is that excitons are formed on the phosphorescent body, and then the energy is transferred to the phosphorescent illuminant and finally released in the form of light. This puts high demands on the design of phosphorescent host materials.
  • commercial OLEDs have gradually occupied the display and lighting industry.
  • the efficiency and stability of red and green phosphorescent host materials have basically met the requirements of display and illumination.
  • blue phosphorescent materials have always been the bottleneck of organic electroluminescent devices.
  • the design principles of blue phosphorescent host materials include the following: 1. The triplet energy level is larger than the guest to achieve effective exciton energy transfer; 2. The HOMO and LUMO energy levels with adjacent layers are Reduce the energy barrier of carrier injection; 3. Match the hole and electron mobility; 4. Good thermal stability and film formation.
  • the researchers made many meaningful attempts and developed different kinds of phosphorescent host materials.
  • the benzimidazole group has strong tensile electron characteristics, strong modification, good electron injection and transmission characteristics, and is suitable as a blue phosphorescent host material.
  • the present invention provides a benzimidazole derivative
  • the object, the preparation method and the application thereof are aimed at synthesizing the benzimidazole derivative and applying it to the electroluminescent device by using a simple and feasible synthesis scheme, thereby solving the poor stability and efficiency of the prior art blue phosphorescent device. Low technical issues.
  • the present invention provides an organic light emitting device including a substrate, an anode layer, a hole injection layer, a hole transport layer, an exciton blocking layer, an organic light emitting layer, and an electron from bottom to top. a transport layer, an electron injecting layer, and a cathode layer; wherein the organic light emitting layer material comprises a benzimidazole derivative represented by Formula 1,
  • P 1 , P 2 and P 3 are a benzene ring, and at least one of R 1 to R 12 is a substituent group having a hole transporting ability.
  • the substituent group having a hole transporting ability is selected from a heterocyclic group having 5 to 65 carbon atoms, or an aromatic group having 6 to 65 carbon atoms, a polycyclic group, and a subaromatic group. a group or a subaromatic heterocyclic group.
  • R 1 to R 12 are selected from the group consisting of hydrogen, phenyl, p-tolyl, diaza-9-carbazolyl, triphenylsilyl, p-triphenylamino, dimethyl-p-triphenylamine, Second-generation tert-butylcarbazolyl, 1-naphthalene-substituted p-triphenylamine, 2-naphthalene-substituted p-triphenylamine, 3,6-di-tert-butylcarbazole phenyl, di-generation 3,6-di-tert-butyl Carbazole phenyl, p-triphenylamino, dimethyl-p-triphenylamine, 1-naphthalene-substituted p-triphenylamine, 2-naphthalene-substituted p-triphenylamine, 2-dibenzothiophene, 3-dibenzothiophene, 4-
  • the organic light-emitting layer further comprises a dopant
  • the dopant is bis(4,6-difluorophenylpyridine-N, C2) pyridine formyl ruthenium, or acetylacetonate bis (2- Phenylbenzothiazole-C2,N) ruthenium (III); the dopant accounts for 0.5 to 7 wt% of the mass of the organic light-emitting layer.
  • the dopant bis(2-phenylbenzothiazole-C2,N) ruthenium (III) acetylacetonate occupies the The mass fraction of the organic light-emitting layer is 0.5 to 5 wt%.
  • the anode layer is made of a semiconductor conductive film; the hole injection layer is made of molybdenum oxide; and the hole transport layer is made of N, N'-diphenyl-N, N'-(1-naphthyl).
  • the exciton barrier material Is N,N'-dicarbazole-3,5-benzene (mCP) or 4,4',4"-tris(carbazol-9-yl)triphenylamine
  • the electron transport layer is made of 1,3 , 5-tris[(3-pyridyl)-3-phenyl]benzene
  • the electron injecting layer is made of LiF
  • the cathode layer is Al.
  • the invention also provides a preparation method of an organic light emitting device, comprising the following steps:
  • a hole injection layer, a hole transport layer, and an exciton blocking layer are sequentially formed on the anode layer by a vacuum thermal evaporation method.
  • the organic light-emitting layer material comprising a benzimidazole derivative represented by Formula 1,
  • P 1 , P 2 , and P 3 are a benzene ring, and at least one of R 1 to R 12 is a substituent group having a hole transporting ability;
  • An electron transport layer, an electron injection layer, and a cathode layer are formed on the organic light-emitting layer by a vacuum thermal evaporation method.
  • the substituent group having a hole transporting ability is selected from a heterocyclic group having 5 to 65 carbon atoms, or an aromatic group having 6 to 65 carbon atoms, a polycyclic group, and a subaromatic group. a group or a subaromatic heterocyclic group.
  • R 1 to R 12 are selected from the group consisting of hydrogen, phenyl, p-tolyl, diaza-9-carbazolyl, triphenylsilyl, p-triphenylamino, dimethyl-p-triphenylamine, Second-generation tert-butylcarbazolyl, 1-naphthalene-substituted p-triphenylamine, 2-naphthalene-substituted p-triphenylamine, 3,6-di-tert-butylcarbazole phenyl, di-generation 3,6-di-tert-butyl Carbazole phenyl, p-triphenylamino, dimethyl-p-triphenylamine, 1-naphthalene-substituted p-triphenylamine, 2-naphthalene-substituted p-triphenylamine, 2-dibenzothiophene, 3-dibenzothiophene, 4-
  • the organic light-emitting layer further comprises a dopant
  • the dopant is bis(4,6-difluorophenylpyridine-N, C2) pyridine formyl ruthenium, or acetylacetonate bis (2- Phenylbenzothiazole-C2,N) ruthenium (III); the dopant accounts for 0.5 to 7 wt% of the mass of the organic light-emitting layer.
  • the benzimidazole group has strong tensile properties, it has strong modification and good electron injection and transmission characteristics, and is suitable as a phosphorescent host material, HOMO/LUMO electron cloud distribution;
  • the present invention has the following advantages:
  • the benzimidazole derivative provided by the present invention has the advantages of simple structure and high triplet energy level with respect to the carbazole-substituted host material, and can realize efficient energy transfer of the triplet excitons from the host to the guest.
  • the benzimidazole derivatives provided by the present invention have balanced carrier mobility, can effectively combine holes and electrons in the light-emitting region, and increase the luminous efficiency of the device.
  • the benzimidazole derivatives provided by the present invention have small steric hindrance, can significantly increase the glass transition temperature and thermal stability, and can improve the service life of the light-emitting device.
  • the blue phosphorescent OLED device provided with the benzimidazole derivative as the light-emitting layer provided by the invention has excellent performance, and the current efficiency, power efficiency and external quantum efficiency can reach the higher performance of the current blue phosphorescent device. Level.
  • the white phosphorescent OLED device using mNBICz as a light-emitting layer provided by the present invention has excellent performance, current efficiency, power efficiency and external quantum efficiency can reach a high level in the performance of current white phosphorescent devices.
  • the benzimidazole derivatives proposed by the present invention can be used in the field of display and illumination.
  • Embodiment 1 is a schematic structural view of an organic light emitting device according to Embodiment 1 of the present invention.
  • Example 2 is a UV-Vis (a) and PL spectrum (b) of mNBICz and pNBICz in a toluene solution in Example 1 of the present invention.
  • Figure 3 is a low temperature phosphorescence emission spectrum of mNBICz and pNBICz in 77K liquid nitrogen according to Example 1 of the present invention.
  • Fig. 4 is a view showing the energy levels of respective compounds in the organic light-emitting devices A and B of Example 1 of the present invention.
  • Figure 5 is a time-spectrum curve of mNBICz in Example 1 of the present invention (a) hole (b) electron; (c) hole and electron mobility curve.
  • Figure 6 is a representation of an electroluminescent device of mNBICz and pNBICz in Example 1 of the present invention: (a) L-V-J curve; (b) efficiency-luminance relationship diagram; (c) EL spectrum.
  • Fig. 7 is a view showing the energy levels of respective compounds in the organic light-emitting devices C and D of Example 2 of the present invention.
  • Figure 8 is a graph showing the data of an electroluminescent device of the organic light-emitting device C, D of Embodiment 2 of the present invention: (a) LVJ curve; (b) relationship between efficiency and luminance; (c) EQE and luminance curve; (d): EL spectrum.
  • Embodiment 9 is a white light device characterization of mNBICz in Embodiment 3 of the present invention: (a) LVJ curve; (b) efficiency and brightness; (c) brightness-external quantum efficiency curve, the inserted picture is the EL of the device under different bias voltages. spectrum.
  • Fig. 10 is a view showing the energy levels of the respective compounds of the organic light-emitting device 1, the organic light-emitting device J, and the organic light-emitting device K in the fourth embodiment of the present invention.
  • Figure 11 is a device characterization of oBITP, mBITP and pBITP blue phosphorescent host materials in Example 4 of the present invention: (a) LVJ curve of the phosphorescent device; (b) graph of efficiency versus luminance in the phosphorescent device; (c) phosphorescent device EL spectrum.
  • the organic light-emitting device provided by the invention has the organic light-emitting layer prepared by using a highly efficient electrophosphorescent material, thereby solving the technical problem that the blue phosphorescent device of the prior art has poor stability and low efficiency.
  • the present embodiment provides an organic light emitting device including an anode layer 10 , a hole injection layer 20 , a hole transport layer 30 , an exciton blocking layer 40 , an organic light emitting layer 50 , and an electron from bottom to top.
  • the anode layer is made of a semiconductor conductive film (ITO); the hole injection layer is made of molybdenum oxide (MoO 3 ); and the hole transport layer is made of N, N'-diphenyl-N, N. '-(1-Naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) or 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl) Aniline] (TAPC); the exciton barrier layer is made of N,N'-dicarbazole-3,5-benzene (mCP); the electron transport layer is made of 1,3,5-three [(3) Pyridyl)-3-phenyl]benzene (TmPyPB); the electron injecting layer is made of LiF; and the cathode layer is Al.
  • ITO semiconductor conductive film
  • the hole injection layer is made of molybdenum oxide (MoO 3 )
  • the hole transport layer is made of
  • the organic light-emitting layer material comprises a benzimidazole derivative represented by Formula 1.
  • a benzimidazole derivative represented by Formula 1 in order to suppress the quenching process of triplet-triplet excitons in a device at a high concentration, electrophosphorescent devices generally employ a host-guest doped device structure. Therefore, the benzimidazole derivative, as a host material, further includes a dopant as an object material, and is vapor-deposited at a certain ratio.
  • the dopant can be, for example, bis(4,6-difluorophenylpyridine-N,C2)pyridine hydrazide (FIrpic).
  • P 1 , P 2 and P 3 are a benzene ring, and at least one of R 1 to R 12 is a substituent group having a hole transporting ability, and the rest may be H.
  • a substitution reaction may occur at any position of the benzene rings P 1 , P 2 , and P 3 to modify a substituent having a hole transporting ability.
  • a substituent having a hole transporting ability is formed on a benzene ring, the probability that the other substituent will undergo a substitution reaction again on the benzene ring will be lowered.
  • R 1 to R 12 are each independently H or a heterocyclic group having 5 to 65 carbon atoms or the following groups having 6 to 65 carbon atoms: an aromatic group, a polycyclic group, a subaromatic group or a subaromatic heterocyclic group.
  • R 1 to R 12 may be specifically selected from any one of the substituent groups in Table 1.
  • the substituent No. 15 in Table 1 is used as a substituent group on the P 2 benzene ring to form two stable blue phosphorescent materials as a host of the organic light-emitting layer, 3-carbazolyl-C-phenylbenzimidazole.
  • Base benzene such as formula 2)
  • 4-oxazolyl-C-phenylbenzimidazolyl benzene such as formula 3
  • mNBICz 4-oxazolyl-C-phenylbenzimidazolyl benzene
  • pNBICz 4-oxazolyl-C-phenylbenzimidazolyl benzene
  • Step A Obtaining 4-bromo-N-phenylo-nitroaniline.
  • Step B Obtaining N-(4-bromophenyl)-o-phenylenediamine.
  • Step C Obtainment of C-phenyl-1-p-bromophenylbenzimidazole.
  • Step D 4-oxazolyl-C-phenylbenzimidazolylbenzene (pNBICz).
  • Step A replacement of p-bromoaniline to m-bromoaniline, the other reaction methods are the same
  • Step B obtaining C-phenyl-1-m-bromophenylbenzimidazole in step C, and reacting the C-phenyl-1-m-bromophenylbenzimidazole with carbazole in step D
  • UV-Vis (a) and PL spectra (b) of mNBICz and pNBICz in a toluene solution The Eg of the two compounds can be calculated from Fig. 2 as mNBICz (3.57 eV) and pNBICz (3.51 eV), respectively.
  • mNBICz 3.57 eV
  • pNBICz 3.51 eV
  • the maximum emission peak is at 344 nm, and there is a shoulder at 360 nm, indicating that both compounds have a certain degree of intramolecular energy transfer.
  • the host material is mNBICz
  • the organic light-emitting device is obtained as A
  • the host material is pNBICz
  • the organic light-emitting device is obtained as B.
  • Both organic light-emitting devices were obtained by the following methods: ITO glass was ultrasonically cleaned in a cleaning agent and deionized water for 30 minutes. Then, it was vacuum-dried for 2 hours (105 ° C), and the ITO glass was placed in a plasma reactor for 1 minute of CFx plasma treatment, and transferred to a vacuum chamber to prepare an organic film and a metal electrode.
  • mNBICz was prepared as a host material by vacuum evaporation.
  • the energy level diagrams of the respective compounds of the organic light-emitting device A and the organic light-emitting device B show that the structures of the two organic light-emitting devices obtained can be from bottom to top:
  • Organic light-emitting device A ITO/MoO 3 (thickness: 10 nm) / NPB (thickness: 40 nm) / mCP (thickness: 5 nm) / Host: 6 wt% of FIrpic (thickness: 20 nm) / TmPyPB (thickness: 40 nm) / LiF ( a thickness of 1 nm) / Al (thickness of 100 nm), wherein Host is mNBICz;
  • Organic light-emitting device B ITO/MoO 3 (thickness: 10 nm) / NPB (thickness: 40 nm) / mCP (thickness: 5 nm) / Host: 6 wt% of FIrpic (thickness: 20 nm) / TmPyPB (thickness: 40 nm) / LiF ( a thickness of 1 nm) / Al (thickness of 100 nm), wherein Host is pNBICz;
  • 6wt% indicates that the amount of the dopant FIrpic is 6% of the host material mass fraction.
  • FIG. 6 Characterization of electroluminescent devices of mNBICz and pNBICz.
  • mNBICz and pNBICz show good efficiency in the vapor deposition device, the current efficiency ⁇ CE,max reached 35.7 and 30.9 cd/A, respectively, and the power efficiency ⁇ PE,max reached respectively.
  • the external quantum efficiency EQE max reached 17.3% and 15.1%, respectively.
  • the carbazole-substituted N-position benzimidazole-based phosphorescent host compound is suitable for use as a host material in a small molecule vapor-deposited blue phosphorescent device. More importantly, the roll-off of the two devices at high current densities is also relatively small. It can be seen from the figure that the electroluminescence spectra of mNBICz and pNBICz only have emission peaks at 476 nm and 500 nm, which is the characteristic emission peak of the guest material FIrpic.
  • the organic light-emitting device A and the organic light-emitting device B have a CIE of (0.15, 0.35) at a voltage of 8 V, and both conform to the color coordinate constant of sky blue phosphorescence.
  • This embodiment further optimizes the structure of the organic light emitting device.
  • the organic light-emitting device of the present embodiment uses 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline] (TAPC) instead of NPB for hole transport.
  • Layer, 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA) is used as an exciton barrier layer
  • TCTA 4,4',4"-tris(carbazol-9-yl)triphenylamine
  • mCP is used as a reference. Referring to FIG. 7, the energy level diagrams of the respective compounds of the organic light-emitting devices C and D show that the structure is as follows:
  • Organic light-emitting device C ITO/MoO 3 (10 nm) / TAPC (60 nm) / TCTA (5 nm) / Host: FIrpic (7 wt%, 20 nm) / TmPyPB (35 nm) / LiF (1 nm) / Al (100 nm), wherein the main body Host is mNBICz;
  • Organic light-emitting device D ITO/MoO 3 (10 nm) / TAPC (60 nm) / TCTA (5 nm) / Host: FIrpic (7 wt%, 20 nm) / TmPyPB (35 nm) / LiF (1 nm) / Al (100 nm).
  • the main host is mCP.
  • V on starting voltage
  • L max maximum brightness
  • V voltage at maximum brightness
  • ⁇ c current efficiency
  • ⁇ p power efficiency
  • CIE [x, y] international color coordinate
  • c test voltage It It is 8V.
  • Figure 8 shows the electroluminescent device data curves for device C and device D: (a) LVJ curve; (b) efficiency vs. brightness; (c) EQE versus brightness curve; (d) EL spectrum.
  • the organic light-emitting device C had a turn-on voltage of 3.3 V and a maximum light-emitting luminance of 47,995 cd/m 2 , and this data was measured at an operating voltage of 11.9V.
  • the EQE max of the organic light-emitting device C reached 26.2%, and ⁇ CE,max and ⁇ PE,max were 54.5 cd/A and 52.2 lm/W, respectively.
  • the corresponding organic light-emitting device D has a turn-on voltage of 3.65 V, a maximum luminance of 9093 cd/m 2 , an EQE max of 13.3%, and ⁇ CE,max and ⁇ PE,max of 27.7 cd/A and 24.7 lm/W, respectively. .
  • the structure of the organic light-emitting device C exhibits superior quality.
  • a structure of a single-substitute complementary color white light organic light-emitting device is further prepared.
  • the blue light object still adopts FIrpic
  • the orange light guest uses bis(2-phenylbenzothiazole-C2,N) ruthenium (III) acetylacetonate (III) ( Ir(bt)2(acac)), and the stability of the white light organic light-emitting device was evaluated by adjusting the doping concentration of the orange light guest.
  • the structures of the two organic light-emitting devices E, F, G, and H are as follows:
  • Organic light-emitting device F
  • Organic light-emitting device H
  • This embodiment also analyzes the performance of the above four organic light-emitting devices, as shown in Table 3:
  • V on starting voltage
  • L max maximum brightness
  • V voltage at maximum brightness
  • ⁇ c current efficiency
  • ⁇ p power efficiency
  • CIE [x, y] international color coordinate
  • c test voltage It It is 8V.
  • the organic light-emitting device G has the highest luminous efficiency, ⁇ CE,max reaches 62.5 cd/A, ⁇ PE, max 60.4 lm/W, EQE max 22.9%, and the starting voltage is only 3.3V. Therefore, it can be said that when the doping concentration of Ir(bt) 2 (acac) is 1.5%, it is optimal, but as the doping concentration changes, the efficiency of each device does not change significantly, indicating that the performance of each device is stable. In addition, the maximum luminous brightness of the four white light devices exceeds 48000 cd/m 2 , which meets the needs of practical applications. Like the blue-light device, the matching bipolar transmission characteristics of the host material mNBICz play a crucial role.
  • the color rendering index CRI is only from 60.3 to 62.4. It can be said that the light color is very stable. In summary, the efficiency, luminous intensity, and spectral stability of the white light device EH have reached a satisfactory level.
  • This embodiment provides a method for preparing another benzimidazole derivative as a material of the organic light-emitting layer.
  • the preparation process of oBITP was similar to the preparation process of mBITP, and finally purified by column chromatography to obtain a white solid powder in a yield of 60%.
  • the physical and chemical parameters of the white solid powder are:
  • Embodiment 1 The process steps for preparing an organic light-emitting device using the above three materials can be referred to in Embodiment 1.
  • the energy level diagrams of the compounds of the organic light-emitting device I and the organic light-emitting device J and K show that the structures of the three organic light-emitting devices obtained can be from bottom to top:
  • Organic light-emitting device I ITO/MoO 3 (thickness: 10 nm) / NPB (thickness: 40 nm) / mCP (thickness: 5 nm) / Host: 6 wt% of FIrpic (thickness: 20 nm) / TmPyPB (thickness: 40 nm) / LiF ( a thickness of 1 nm) / Al (thickness of 100 nm), wherein Host is oBITP;
  • Organic light-emitting device J ITO/MoO 3 (thickness: 10 nm) / NPB (thickness: 40 nm) / mCP (thickness: 5 nm) / Host: 6 wt% of FIrpic (thickness: 20 nm) / TmPyPB (thickness: 40 nm) / LiF ( a thickness of 1 nm) / Al (thickness of 100 nm), wherein Host is mBITP;
  • Organic light-emitting device K ITO/MoO 3 (thickness: 10 nm) / NPB (thickness: 40 nm) / mCP (thickness: 5 nm) / Host: 6 wt% of FIrpic (thickness: 20 nm) / TmPyPB (thickness: 40 nm) / LiF ( The thickness is 1 nm) / Al (thickness is 100 nm), where Host is pBITP.
  • Figure 11 shows device characterization of oBITP, mBITP and pBITP blue phosphorescent host materials: (a) L-V-J curve for phosphorescent devices; (b) efficiency versus luminance for phosphorescent devices; and (c) EL spectra for phosphorescent devices.
  • the turn-on voltages of the three devices are 3.3, 3.6, and 3.6V, respectively.
  • the organic light-emitting device I and the organic light-emitting device J exhibited good efficiency under evaporation conditions, and ⁇ CE,max reached 30.1 cd/A and 31.5 cd/A, respectively, and ⁇ PE,max reached 22.4 lm/W and 28.4 lm/ respectively.
  • the efficiency of the organic light-emitting device K is very low, which may be due to the large electron injection energy barrier and the low triplet energy level, which cannot effectively limit the excitons to the light-emitting layer.
  • the HOMO and LUMO levels of oBITP and mBITP are relatively close, and the triplet energy levels of both are higher than 2.80 eV.
  • the host material the energy transfer between the host and the guest can be well realized. This indicates that oBITP and mBITP are more suitable as blue phosphorescent host materials than pBITP.
  • aVon start voltage
  • Lmax maximum brightness
  • V voltage at maximum brightness
  • ⁇ c current efficiency
  • ⁇ p power efficiency
  • CIE[x, y] international color coordinate
  • c test voltage is 8V.
  • the EL spectra of the organic light-emitting devices I and J both exhibit good emission peaks of the guest FIrpic, and the CIE coordinates are (0.14, 0.30) and (0.15, 0.36), respectively, and under different voltages. Stable, this confirms that the triplet excitons of these two materials can be completely delivered to the guest material.
  • the triplet energy level is only 2.72 eV due to the greater degree of conjugation between the two benzenes connected by the para position, which is only slightly higher than the triplet energy of the guest FIrpic. Level, can not guarantee the complete transfer of triplet energy.

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Abstract

一种有机发光器件及其制备方法，从下至上包括：衬底、阳极层（10）、空穴注入层（20）、空穴传输层（30）、激子阻隔层（40）、有机发光层（50）、电子传输层（60）、电子注入层（70）和阴极层（80）；有机发光层材料包括式1所示的苯并咪唑衍生物，式1，其中，P1、P2、P3为苯环；R 1～R 12至少一个为具有空穴传输能力的取代基团。该苯并咪唑类衍生物相对于双咔唑取代的主体材料结构简单，三重态能级高，能够实现三重态激子由主体到客体有效的能量转移。

Description

一种有机发光器件及其制备方法 技术领域
本发明属于柔性显示技术领域，具体地讲，涉及一种有机发光器件的制备。
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(Appl.Phys.Lett.,1987,52,913)。1990年，Burroughes等人发现了以共轭高分子PPV为发光层的OLED(Nature.1990,347,539)，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(Appl.Phys.Let.,1999,75,4.)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。
由于三重态激子的寿命较长，为了抑制在高浓度下器件中三重态-三重态激子的湮灭过程，因此电致磷光器件一般都采用主客体掺杂的器件结构，即利用磷光主体材料掺杂一定百分比的磷光客体材料作为发光层。器件的发光机理为主客体的能量转移方式或者载流子在客体上的直接捕获方式。前一种方式是激子在磷光主体上形成，然后将能量传递给磷光客发光体最后以光的形式放出。这就对于磷光主体材料的设计提出了很高的要求。目前，目前商业化的OLED已经逐步占领显示和照明产业。红色与绿色磷光主体材料的效率及其稳定性都已基本满足了显示和照明的需求，然而蓝色磷光材料一直是有机电致发光器件的瓶颈。
总的来说，蓝色磷光主体材料的设计原则包括以下几点：1.三重态能级大于客体以实现有效的激子能量转移；2.具有与相邻层匹配的HOMO与LUMO能级以减小载流子注入的能垒；3.有匹配的空穴与电子迁移率；4.良好的热稳定性与成膜性。为了在同种分子中，同时实现这三种不同的要求，研究人员进行了很多有意义的尝试，并且开发出不同种类的磷光发光主体材料。其中，苯并咪唑基团表现较强的拉电子特性，修饰性较强，具有较好的电子注入和传输特性，适合作为蓝色磷光主体材料。
2011年，台湾大学Ken-Tsung Wong教授课题组报道了一组将9-苯基咔唑的3位与苯并咪唑直接相连的磷光主体材料，结构如图1所示。结果表明通过改变了苯并咪唑的连接位置能够有效地改变分子的共轭程度并调节分子的激发态能级(参考[1]Chen Y M,Hung W Y,You H W,et al.Carbazole–benzimidazole hybrid bipolar host materials for highly efficient green and blue phosphorescent OLEDs.Journal of Materials Chemistry,2011,21(38):14971～14978.)。
Figure PCTCN2017089607-appb-000001
但是，同时应该指出的是，该系列材料的发光效率仍然比较低，其中以mCPNBI为主体的器件获得了最大的蓝光发光效率，但是最大外部量子效率、电流效率和功率效率仍然只有16.3％,35.7cd/A和23.3lm/W，仍然无法满足显示和照明的需求。
发明内容
针对现有技术的以上缺陷或改进需求，本发明提供了一种苯并咪唑类衍生 物、制备方法及其应用，其目的在于通过采用简单可行的合成方案合成苯并咪唑类衍生物并将其应用于电致发光器件，由此解决现有技术的蓝色磷光器件稳定性差、效率低的技术问题。
为了解决上述现有技术存在的问题，本发明提供一种有机发光器件，从下至上包括：衬底、阳极层、空穴注入层、空穴传输层、激子阻隔层、有机发光层、电子传输层、电子注入层和阴极层；其中，所述有机发光层材料包括式1所示的苯并咪唑衍生物，
Figure PCTCN2017089607-appb-000002
其中，P1、P2、P3为苯环，R1～R12中至少一个为具有空穴传输能力的取代基团。
其中，所述具有空穴传输能力的取代基团选自碳原子个数为5～65的杂环基团，或者碳原子个数为6～65的芳香基团、多环基团、亚芳香基团或亚芳香杂环基团。
其中，所述R1～R12选自氢基、苯基、对甲苯基、二氮杂-9-咔唑基、三苯基硅基、对三苯胺基、二甲基对三苯胺基、二代叔丁基咔唑基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、3，6-二叔丁基咔唑苯基、二代3，6-二叔丁基咔唑苯基、对三苯胺基、二甲基对三苯胺基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、2-二苯并噻吩、3-二苯并噻吩、4-二苯并噻吩、间三联苯基。
其中，所述有机发光层还包括掺杂剂，所述掺杂剂为双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱，或者，乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)；所述掺杂剂占所述有机发光层的质量分数为0.5～7wt％。
其中，所述掺杂剂乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)占所述有 机发光层的质量分数为0.5～5wt％。
其中，所述阳极层材质为半导体导电膜；所述空穴注入层材质为氧化钼；所述空穴传输层材质为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺或者4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]；所述激子阻隔层材质为N,N′-二咔唑-3,5-苯(mCP)或者4,4',4″-三(咔唑-9-基)三苯胺；所述电子传输层的材质为1,3,5-三[(3-吡啶基)-3-苯基]苯；所述电子注入层的材质为LiF；所述阴极层为Al。
本发明还提供一种有机发光器件的制备方法，包括如下步骤：
在衬底上形成阳极层；
采用真空热蒸镀方法，在所述阳极层依次形成空穴注入层、空穴传输层、激子阻隔层，
采用真空热蒸镀方法，在所述激子阻隔层上形成有机发光层，所述有机发光层材料包括式1所示的苯并咪唑衍生物，
Figure PCTCN2017089607-appb-000003
其中，P1、P2、P3为苯环，R1～R12中至少一个为具有空穴传输能力的取代基团；
再利用真空热蒸镀方法在所述有机发光层上形成电子传输层、电子注入层和阴极层。
其中，所述具有空穴传输能力的取代基团选自碳原子个数为5～65的杂环基团，或者碳原子个数为6～65的芳香基团、多环基团、亚芳香基团或亚芳香杂环基团。
其中，所述R1～R12选自氢基、苯基、对甲苯基、二氮杂-9-咔唑基、三苯基硅基、对三苯胺基、二甲基对三苯胺基、二代叔丁基咔唑基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、3，6-二叔丁基咔唑苯基、二代3，6-二叔丁基咔唑苯基、对三苯胺基、二甲基对三苯胺基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、2-二苯并噻吩、3-二苯并噻吩、4-二苯并噻吩、间三联苯基。
其中，所述有机发光层还包括掺杂剂，所述掺杂剂为双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱，或者，乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)；所述掺杂剂占所述有机发光层的质量分数为0.5～7wt％。
有益效果：
由于苯并咪唑基团表现较强的拉电子特性，修饰性较强，具有较好的电子注入和传输特性，适合作为磷光主体材料，HOMO/LUMO电子云分布；
因此，本发明具有如下优点：
(1)本发明所提供的苯并咪唑类衍生物相对于双咔唑取代的主体材料具有结构简单，三重态能级高的优点，能够实现三重态激子由主体到客体有效的能量转移。
(2)本发明所提供的苯并咪唑类衍生物具有平衡的载流子迁移率，能够实现空穴和电子在发光区的有效复合，增大器件的发光效率。
(3)本发明所提供的苯并咪唑类衍生物具有较小的空间位阻，可以显著提高玻璃化转变温度和热稳定性，能够提高发光器件的使用寿命。
(4)本发明所提供的以苯并咪唑类衍生物作为发光层的蓝色磷光OLED器件性能优异，电流效率，功率效率和外量子效率均能达到目前蓝色磷光器件的性能中的较高水平。
(5)本发明所提供的以mNBICz作为发光层的白色磷光OLED器件性能优异，电流效率，功率效率和外量子效率均能达到目前白色磷光器件的性能中的较高水平。
(6)本发明提出的苯并咪唑类衍生物可以用于显示和照明领域。
附图说明
通过结合附图进行的以下描述，本发明的实施例的上述和其它方面、特点和优点将变得更加清楚，附图中：
图1是本发明实施例1的有机发光器件结构示意图。
图2是本发明实施例1中mNBICz和pNBICz在甲苯溶液中的UV-Vis(a)及PL光谱(b)。
图3是本发明实施例1在77K液氮中，mNBICz和pNBICz的低温磷光发射光谱。
图4是本发明实施例1有机发光器件A、B中各化合物的能级示意图。
图5是本发明实施例1中mNBICz的时间光谱曲线(a)空穴(b)电子；(c)空穴和电子迁移率曲线图。
图6是本发明实施例1中mNBICz和pNBICz的电致发光器件表征：(a)L-V-J曲线；(b)效率-亮度关系图；(c)EL光谱。
图7是本发明实施例2有机发光器件C、D中各化合物的能级示意图。
图8是本发明实施例2有机发光器件C、D的电致发光器件数据曲线：(a)L-V-J曲线；(b)效率与亮度关系图；(c)EQE与亮度曲线；(d)：EL光谱。
图9是本发明实施例3中mNBICz的白光器件表征：(a)L-V-J曲线；(b)效率与亮度；(c)亮度-外量子效率曲线，插入的图片为器件在不同偏压下的EL光谱。
图10是本发明实施例4中有机发光器件I和有机发光器件J、有机发光器件K各化合物能级示意图。
图11是本发明实施例4中oBITP,mBITP和pBITP蓝色磷光主体材料的器件表征：(a)磷光器件的L-V-J曲线；(b)磷光器件中效率与亮度关系图；(c)磷光器件的EL光谱。
具体实施方式
以下，将参照附图来详细描述本发明的实施例。然而，可以以许多不同的形式来实施本发明，并且本发明不应该被解释为限制于这里阐述的具体实施例。相反，提供这些实施例是为了解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够理解本发明的各种实施例和适合于特定预期应用的各种修改。
本发明提供的有机发光器件，其有机发光层是采用高效的电致磷光材料制备，由此解决现有技术的蓝色磷光器件稳定性差、效率低的技术问题。
实施例1
如图1所示，本实施例提供一种有机发光器件，其从下至上包括：阳极层10、空穴注入层20、空穴传输层30、激子阻隔层40、有机发光层50、电子传输层60和电子注入层70、阴极层80。
其中，所述阳极层材质为半导体导电膜(ITO)；所述空穴注入层材质为氧化钼(MoO3)；所述空穴传输层材质为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(NPB)或者4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)；所述激子阻隔层材质为N,N′-二咔唑-3,5-苯(mCP)；所述电子传输层的材质为1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPB)；所述电子注入层的材质为LiF；所述阴极层为Al。
其中，所述有机发光层材料包括式1所示的苯并咪唑衍生物。优选地，为了抑制在高浓度下器件中三重态-三重态激子的湮灭过程，电致磷光器件一般都采用主客体掺杂的器件结构。因此，苯并咪唑衍生物作为主体(Host)材料之余，还包括有掺杂剂作为客体(Object)材料，按照一定比例一并蒸镀。掺杂剂可例如为双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱(FIrpic)。
Figure PCTCN2017089607-appb-000004
其中，P1、P2、P3为苯环，R1～R12中至少一个为具有空穴传输能力的取代基团，其余可为H。
理论上，苯环P1、P2、P3任何位置均有可能发生取代反应，修饰具有空穴传输能力的取代基。实际上一个苯环上一旦形成有空穴传输能力的取代基，将降低其他取代基在该苯环上再次发生取代反应的几率。
若形成二位取代，一方面有可能会增大其电子的离域分布范围，降低其三重态，另一方面在同一个苯环上进行修饰会造成位阻增加，影响其结构的稳定性。故此，由于取代位阻和电子云结构限制，在实际应用中P1、P2或P3上较多的情况是只有一种除H之外的其它取代基团。
具体地，R1～R12各自独立地为H或者碳原子个数为5～65的杂环基团或碳原子个数为6～65的以下基团：芳香基团、多环基团、亚芳香基团或亚芳香杂环基团。
例如，R1～R12可具体选自表1中的任一项取代基团。
表1：R1～R12各取代基的结构和名称
Figure PCTCN2017089607-appb-000005
Figure PCTCN2017089607-appb-000006
Figure PCTCN2017089607-appb-000007
例如，采用表1中第15号取代基作为P2苯环上的取代基团形成两种稳定蓝磷光材料作为有机发光层的主体(Host)，3-咔唑基-C-苯基苯并咪唑基苯(如式2)、4-咔唑基-C-苯基苯并咪唑基苯(如式3)，分别简称为mNBICz、pNBICz：
Figure PCTCN2017089607-appb-000008
下面，介绍所述的苯并咪唑衍生物mNBICz和pNBICz的制备过程，pNBICz和mNBICz的制备方法是雷同的，制备路线如方程式1所示：
Figure PCTCN2017089607-appb-000009
方程式1
具体以所述C-苯基-1-对溴苯基苯并咪唑pNBICz的制备步骤为例，如下：
步骤A:4-溴-N-苯基邻硝基苯胺的获得。
在干燥的圆底烧瓶中，将邻氟硝基苯(4.40g,31.7mmol)，对溴苯胺(10.9g,63.4mmol)和无水氟化钾(2.30g,39.6mmol)的混合物加入其中，在氮气保护下加热到150℃，回流24小时。反应结束后，将产物溶于二氯甲烷中，并用水洗涤三次，用无水硫酸钠干燥后，旋干，产物用甲醇重结晶，得到最终产物为橘红色的针状晶体5.7g,产率61％。
最终产物的物化参数为：1H NMR(400MHz,CDCl3,δ):9.39(s,1H),8.21(d,J＝7.6Hz,1H),7.53(d,J＝7.6Hz,2H),7.39(t,J＝12.4Hz,1H),7.14-7.21(m,3H),6.81(t,J＝12.4Hz,1H).MS(APCI):calcd for C12H9N2O2Br,293.12；found,294.4(M+1)+，可知该最终产物为4-溴-N-苯基邻硝基苯胺。
步骤B:N-(4-溴苯基)-邻苯二胺的获得。
在500ml单口瓶中，将步骤A获得的化合物4-溴-N-苯基邻硝基苯胺(5.70g,19.4mmol)和还原剂氯化亚锡(22.0g,97.0mmol)用250ml无水乙醇溶解，加 热回流反应过夜。反应结束后，蒸干溶剂。然后加入500ml水，并用碳酸氢钠将溶液调至中性。用乙酸乙酯萃取三次，有机层用硫酸钠干燥，然后蒸出溶剂得到粗产物4.1g，产率80％。
所述粗产物的物化参数为：1H NMR(400MHz,CDCl3,δ):7.28(d,J＝7.6Hz,2H),7.01-7.10(m,2H),6.73-6.82(m,2H),6.60(d,J＝7.6Hz,2H),5.18(s,1H),3.75(s,2H).MS(APCI):calcd for C12H11N2Br,263.12；found,264.3(M+1)+，可证实为含有N-(4-溴苯基)-邻苯二胺。
步骤C：C-苯基-1-对溴苯基苯并咪唑的获得。
将步骤B获得的N-(4-溴苯基)-邻苯二胺(4g,14.4mmol)溶解于冰乙酸(100ml)中，120℃下反应过夜，蒸干其中的冰醋酸得到棕色固体粉末23.6g，产率：98％。棕色固体粉末的物化参数为：1H-NMR(DMSO-d6,400MHz):δ(ppm)7.82～7.80(d,J＝7.6Hz,1H),7.62～7.54(m,5H),7.46～7.44(m,4H),7.35～7.27(m,2H),7.21～7.19(d,J＝7.2Hz,2H)，可证实为C-苯基-1-对溴苯基苯并咪唑。
步骤D：4-咔唑基-C-苯基苯并咪唑基苯(pNBICz)。
在50ml干燥的烧瓶中，将咔唑(1.5g,9mmol),C-苯基-1-对溴苯基苯并咪唑(2.78g,8.0mmol),碘化亚铜(0.046g,0.24mmol),18-冠醚-6(0.064g,0.24mmol),碳酸钾(5.53g,40.0mmol)溶解在DMPU(2ml)中，加热至170℃，在氮气保护下加热到170℃并反应两天。过滤后分别用有机溶剂和水洗涤，最后柱层析得白色产物2.4g,产率：90％。
白色产物的物化参数为：1H-NMR:(CDCl3,600MHz):δ(ppm)8.27～8.29(m,1H),7.89～7.94(dd,J＝6Hz,3H),7.65～7.68(m,2H),7.44～7.45(d,J＝6Hz,1H),7.25～7.28(m,1H),7.01～7.10(m,5H),6.82～6.89(m,4H),6.76～6.78(t,J＝12Hz,2H),6.30～6.31(d,J＝6Hz,2H).13C-NMR(150MHz,CDCl3):δ139.81,136.34,133.97,131.18,128.69,128.31,127.85,127.74,125.62,124.46,123.56,123.26,119.91,119.41,110.29,109.83.MS(APCI):calcd for C31H21N3,435.17；found,436.2(M+1)+.Anal.calcd for C31H21N3(％):C 85.34,H 4.93,N 9.73；found:C 85.90,H 4.20,N 9.90，可证实含有4-咔唑基-C-苯基苯并咪唑基苯。
类似地，重复步骤A(对溴苯胺替换为间溴苯胺，其他反应方法相同)、 步骤B，在步骤C中获得C-苯基-1-间溴苯基苯并咪唑，并在步骤D中利用所述C-苯基-1-间溴苯基苯并咪唑与咔唑反应获得白色产物，产率：88％。
白色产物的物化参数为：1H NMR(400MHz,CDCl3)δ(ppm):7.98～8.00(d,J＝6Hz 2H),7.80～7.84(d,J＝6Hz 1H),7.70～7.75(t,J＝12Hz 1H),7.53～7.62(m,4H),7.32～7.48(m,4H),7.15～7.30(m,7H),6.90～7.00(s,2H).13C NMR(400MHz,CDCl3)δ[ppm]:152.55,142.93,140.48,139.52,138.63,136.81,131.98,130.30,129.96,129.67,128.77,126.67,125.98,125.08,123.73,123.37,120.20,120.05,110.58,109.55.MS(APCI):calcd for C31H21N3,435.17；found,436.1(M+1)+.Anal.calcd for C31H21N3(％):C 85.34,H 4.93,N 9.73；found:C 85.40,H 4.90,N 9.70，可证实含有3-咔唑基-C-苯基苯并咪唑基苯。
结合图2，mNBICz和pNBICz在甲苯溶液中的UV-Vis(a)及PL光谱(b)。从图2可以计算得到2个化合物的Eg分别为mNBICz(3.57eV)和pNBICz(3.51eV)。对于mNBICz和pNBICz的PL光谱，最大发射峰在344nm，在360nm处还有一个肩峰，说明两个化合物都有一定程度的分子内能量转移。
如图3，在77K液氮中，mNBICz和pNBICz的低温磷光发射光谱。从化合物的第一个发射峰可以计算出它们的三重态能级，三重态能级的高低顺序为mNBICz(2.78eV)>pNBICz(2.71eV)。
下面，介绍采用上述两种材料制备有机发光器件的工艺步骤。
采用上述两种材料可形成两种有机发光器件，主体材料为mNBICz，获得有机发光器件为A；主体材料为pNBICz，获得有机发光器件为B。两种有机发光器件均可采用以下方法获得：ITO玻璃相继在清洗剂和去离子水中以超声波清洗30分钟。然后真空干燥2小时(105℃)，再将ITO玻璃放入等离子反应器中进行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。通过真空蒸镀的方法将mNBICz作为主体材料制备成器件。
结合图4所示，有机发光器件A和有机发光器件B各化合物能级示意图可知，所获得的两种有机发光器件的结构从下至上可为：
有机发光器件A：ITO/MoO3(厚度为10nm)/NPB(厚度为40nm)/mCP(厚度为5nm)/Host:6wt％的FIrpic(厚度为20nm)/TmPyPB(厚度为40nm)/LiF(厚 度为1nm)/Al(厚度为100nm)，其中Host为mNBICz；
有机发光器件B：ITO/MoO3(厚度为10nm)/NPB(厚度为40nm)/mCP(厚度为5nm)/Host:6wt％的FIrpic(厚度为20nm)/TmPyPB(厚度为40nm)/LiF(厚度为1nm)/Al(厚度为100nm)，其中Host为pNBICz；
其中，6wt％表示，掺杂剂FIrpic的量为占主体材料Host质量分数为6％。
结合图5所示，其示出了mNBICz的时间光谱曲线(a)空穴(b)电子；(c)空穴和电子迁移率曲线。当电场强度为5.0×105V cm-1时，mNBICz的空穴和电子迁移率分别为4.32×10-5cm2V-1s-1和6.12×10-5cm2V-1s-1。从图中可以看出，在同一电场强度下，mNBICz的电子和空穴迁移率相近，都在10-5量级，并且电子迁移率略高于空穴迁移率；在电场强度变化的情况下，空穴和电子迁移率也会随着电场强度的增大而增大，但是总体来说还是保持在一个稳定的范围之内，并且数值上比较接近。这说明mNBICz同时具有空穴和电子传输性能，并且对两种载流子的传输能力接近，这样有利于激子在发光层的中心复合发光，从而提高复合几率以及量子效率。
图6mNBICz和pNBICz的电致发光器件表征。(a)L-V-J曲线；(b)效率-亮度关系图；(c)EL光谱。从以上图中的器件数据可以看出，mNBICz和pNBICz在蒸镀器件中表现出良好的效率，电流效率ηCE,max分别达到了35.7和30.9cd/A，功率效率ηPE,max分别达到了29.0和21.7lm/W，外量子效率EQEmax分别达到17.3％和15.1％。从发光效率来看，咔唑取代N位苯并咪唑类磷光主体化合物适合于用来作为小分子蒸镀蓝色磷光器件中的主体材料。更为重要的是，两种器件在高电流密度下的滚降也比较小。从图中可以看出，mNBICz和pNBICz的电致发光光谱都只有在476nm和500nm处有发射峰出现，这是客体材料FIrpic的特征发射峰。有机发光器件A和有机发光器件B在8V的电压下的CIE均为(0.15,0.35)，均符合天蓝色磷光的色坐标常数。
实施例2
本实施例进一步优化有机发光器件的结构。与实施例1相比，本实施例的有机发光器件中采用4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)代替NPB用作空穴传输层、4,4',4″-三(咔唑-9-基)三苯胺(TCTA)用作激子阻隔层，并用 传统的磷光材料mCP作为参比。结合图7所示，有机发光器件C和D各化合物能级示意图可知，形成的结构如下：
有机发光器件C：ITO/MoO3(10nm)/TAPC(60nm)/TCTA(5nm)/Host:FIrpic(7wt％,20nm)/TmPyPB(35nm)/LiF(1nm)/Al(100nm)，其中主体Host为mNBICz；
有机发光器件D：ITO/MoO3(10nm)/TAPC(60nm)/TCTA(5nm)/Host:FIrpic(7wt％,20nm)/TmPyPB(35nm)/LiF(1nm)/Al(100nm)。其中主体Host为mCP。
参见表2所示，其示出了有机发光器件A、B、C和D的性能参数
表2有机发光器件A、B、C和D的性能参数
Figure PCTCN2017089607-appb-000010
aVon:启动电压；Lmax:最大亮度；V:最大亮度时电压；ηc:电流效率；ηp:功率效率；CIE[x,y]:国际色坐标；b最大效率；c测试电压为8V。
图8示出了器件C和器件D的电致发光器件数据曲线：(a)L-V-J曲线；(b)效率与亮度关系图；(c)EQE与亮度曲线；(d)EL光谱。有机发光器件C的开启电压为3.3V，最大发光亮度达到了47995cd/m2，而且这一数据是在操作电压为11.9V时测得的。同时有机发光器件C的EQEmax达到了26.2％,ηCE,max和ηPE,max分别为54.5cd/A和52.2lm/W。与之相对应的有机发光器件D的开启电压为3.65V，最大亮度为9093cd/m2，EQEmax为13.3％,ηCE,max和ηPE,max分别为27.7cd/A和24.7lm/W。有机发光器件C的结构表现更为优秀的品质。
实施例3
本实施例是在实施例2良好的蓝光器件效率基础上，进一步制备一种单一主体互补色的白色光有机发光器件的结构。与实施例2相比，本实施例的有机发光器件中，蓝光客体仍然采用FIrpic，橘黄光客体采用了乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)(Ir(bt)2(acac))，并通过调整橘黄光客体的掺杂浓度，分析评价这种白色光有机发光器件的稳定性。形成两种有机发光器件E、F、G、H的结构如下：
有机发光器件E：
ITO/MoO3(10nm)/TAPC(60nm)/TCTA(5nm)/Host:FIrpic:Ir(bt)2(acac)
(7wt％:0.5wt％，20nm)/TmPyPB(35nm)/LiF(1nm)/Al；其中主体Host为mNBICz；
有机发光器件F：
ITO/MoO3(10nm)/TAPC(60nm)/TCTA(5nm)/Host:FIrpic:Ir(bt)2(acac)
(7wt％:1wt％，20nm)/TmPyPB(35nm)/LiF(1nm)/Al；其中主体Host为mNBICz；
有机发光器件G：
ITO/MoO3(10nm)/TAPC(60nm)/TCTA(5nm)/Host:FIrpic:Ir(bt)2(acac)
(7wt％:1.5wt％，20nm)/TmPyPB(35nm)/LiF(1nm)/Al；其中主体Host为mNBICz；
有机发光器件H：
ITO/MoO3(10nm)/TAPC(60nm)/TCTA(5nm)/Host:FIrpic:Ir(bt)2(acac)
(7wt％:2wt％，20nm)/TmPyPB(35nm)/LiF(1nm)/Al；其中主体Host为mNBICz。
本实施例还分析了上述四种有机发光器件的性能，如表3所示：
表3mNBICz白光器件器件性能
Figure PCTCN2017089607-appb-000011
aVon:启动电压；Lmax:最大亮度；V:最大亮度时电压；ηc:电流效率；ηp:功率效率；CIE[x,y]:国际色坐标；b最大效率；c测试电压为8V。
结合图9所示，从光谱数据可以看出，随着n值的增大，光色是逐渐红移的。有机发光器件G的发光效率最大，ηCE,max达到了62.5cd/A,ηPE,max60.4lm/W,EQEmax22.9％，并且启动电压只有3.3V。因此可以说当Ir(bt)2(acac)的掺杂浓度为1.5％时为最优，但是随着掺杂浓度的变化，各个器件效率并没有发生明显的变化，说明各个器件性能稳定。另外，4个白光器件的最大发光亮度均超过了48000cd/m2，达到了实际应用的需求。和蓝光器件一样，主体材料mNBICz的匹配的双极传输特性起到了至关重要的作用。
从图9还可以看出，随着电压的增加，整个光谱中的475nm处的发射峰是逐渐增强的。这是由于蓝光部分的发射，即客体FIrpic的发射主要来自于主体到客体的三重态能量转移，而橘黄光部分的发射则主要来自于激子在客体Ir(bt)2(acac)上的直接复合发光。而根据文献的报道，电压的增大有利于主体到客体的能量转移，而不利于客体的直接激子捕获，因此会出现这种光谱现象。虽然光谱会随着电压的变化而变化，但是整体变化并不是很大，从5V到10V的操作电压，显色指数CRI也仅仅是从60.3到62.4，可以说光色十分稳定。综上所述，白光器件E-H的效率、发光强度以及光谱的稳定性都已经达到了令人满意的程度。
实施例4
本实施例提供另外几种作为有机发光层材料的苯并咪唑衍生物的制备方法。
例如，采用表1中第14号取代基作为P2苯环上的取代基团形成三种稳定蓝磷光材料作为有机发光层的主体(Host)，如式4、式5和式6所示，分别简称为oBITP,mBITP和pBITP：
Figure PCTCN2017089607-appb-000012
下面，介绍所述的苯并咪唑衍生物oBITP,mBITP和pBITP的制备过程，oBITP,mBITP和pBITP的制备方法是雷同的，制备路线如方程式2所示：
Figure PCTCN2017089607-appb-000013
方程式2
具体以mBITP的制备步骤为例详细展开叙述。
A.mBITP的合成：
在150ml的烧瓶中，将4(0.87g,2.5mmol)，1-硼酸-间三联苯基(2)(1.1g,4mmol)，Pd(PPh3)4(0.11g,0.1mmol),碳酸钾(2.0M)(5.0ml,10.0mmol)，甲苯(25ml)，无水乙醇(15ml)依次加入。氮气保护下，加热到100℃反应12 小时。待反应结束后，冷却至室温，反应体系出现明显的分层现象，上层为黄色液体，下层为无色透明液体。将下层液除去，并将上层溶液蒸出，得到的粗产物通过柱层析的方法提纯得白色固体粉末0.98g，产率80％。
白色固体粉末的物化参数为：1H-NMR:(CDCl3,400MHz):δ(ppm)7.91～7.93(d,J＝8Hz,1H),7.75～7.81(m,3H),7.63～7.70(m,5H),7.34～7.55(m,14H),7.28～7.29(t,J＝4Hz,3H).13C-NMR(100MHz,CDCl3):δ142.36,141.38,140.91,137.11,130.02,129.08,128.88,128.77,128.32,127.62,127.43,125.41,124.97,119.87,110.50。MS(APCI):calcd for C37H26N2:498.5,found,499.6(M+1)+.Anal.calcd for C37H26N2(％):C,89.13；H,5.26；N,5.62；found:C 89.38,H 5.11,N 5.51。
B.oBITP的合成：
oBITP的制备过程和mBITP的制备过程类似，最后通过柱层析提纯得到白色固体粉末，产率：60％。
白色固体粉末的物化参数为：1H-NMR:(CDCl3,400MHz):δ(ppm)7.99～8.18(m,2H),7.53～7.58(m,3H),7.37～7.46(m,2H),6.91～7.28(m,17H),6.52～6.54(d,J＝8Hz,2H).13C-NMR(100MHz,CDCl3):δ142.36,141.38,140.91,130.02,129.08,128.88,128.77,128.32,127.62,127.43,125.41,124.97,123.54,123.17,119.87,110.50.MS(APCI):calcd for C37H26N2:498.4,found,499.5(M+1)+.Anal.calcd for C37H26N2(％):C,89.13；H,5.26；N,5.62；found:C 89.08,H5.21,N 5.71。
C.pBITP的合成：
pBITP的制备过程和mBITP的制备过程类似，最后通过柱层析提纯得到白色固体粉末，产率：86％。
白色固体粉末的物化参数为：
1H-NMR:(CDCl3,400MHz):δ(ppm)7.90～7.92(d,J＝8Hz,1H),7.76～7.77(d,J＝4Hz,3H)7.63～7.70(m,8H),7.45～7.55(m,7H),7.33～7.40(m,5H),7.24～7.27(m,2H).13C-NMR(100MHz,CDCl3):δ151.99,143.03,142.49,141.95,141.19,141.00,137.38,137.08,129.99,129.91,128.87,128.70,127.63,127.53,127.35,127.12,125.65,125.01,123.44,123.10,119.85,110.48.MS(APCI):calcd for C37H26N2: 498.7,found,499.8(M+1)+.Anal.calcd for C37H26N2(％):C,89.13；H,5.26；N,5.62；found:C,88.93；H,5.16；N,5.91。
采用上述三种材料制备有机发光器件的工艺步骤可参阅实施例1所示。
结合图10所示，有机发光器件I和有机发光器件J、K各化合物能级示意图可知，所获得的三种有机发光器件的结构从下至上可为：
有机发光器件I：ITO/MoO3(厚度为10nm)/NPB(厚度为40nm)/mCP(厚度为5nm)/Host:6wt％的FIrpic(厚度为20nm)/TmPyPB(厚度为40nm)/LiF(厚度为1nm)/Al(厚度为100nm)，其中Host为oBITP；
有机发光器件J：ITO/MoO3(厚度为10nm)/NPB(厚度为40nm)/mCP(厚度为5nm)/Host:6wt％的FIrpic(厚度为20nm)/TmPyPB(厚度为40nm)/LiF(厚度为1nm)/Al(厚度为100nm)，其中Host为mBITP；
有机发光器件K：ITO/MoO3(厚度为10nm)/NPB(厚度为40nm)/mCP(厚度为5nm)/Host:6wt％的FIrpic(厚度为20nm)/TmPyPB(厚度为40nm)/LiF(厚度为1nm)/Al(厚度为100nm)，其中Host为pBITP。
图11示出了oBITP,mBITP和pBITP蓝色磷光主体材料的器件表征：(a)磷光器件的L-V-J曲线；(b)磷光器件中效率与亮度关系图；(c)磷光器件的EL光谱。三个器件的开启电压分别是3.3、3.6、3.6V。有机发光器件I和有机发光器件J在蒸镀条件下展现出良好的效率，ηCE,max分别达到了30.1cd/A与31.5cd/A，ηPE,max分别达到了22.4lm/W与28.4lm/W，EQEmax分别达到16％与14.7％。但是有机发光器件K的效率却很低，这可能是由于其电子注入能垒较大，同时三重态能级较低，不能有效地将激子限制在发光层。oBITP与mBITP的HOMO与LUMO能级比较接近，并且两者的三重态能级均高于2.80eV,作为主体材料可以很好地实现主客体能量转移。这说明相对于pBITP，oBITP与mBITP更适合于作为蓝色磷光主体材料。
本实施例对oBITP,mBITP和pBITP作为主体材料制备的有机发光器件性能进行了分析，结果如表4所示。
表4oBITP,mBITP和pBITP作为主体材料制备的有机发光器件性能
Figure PCTCN2017089607-appb-000014
aVon:启动电压；Lmax:最大亮度；V:最大亮度时电压；ηc:电流效率；ηp:功率效率；CIE[x,y]:国际色坐标；b最大效率；c测试电压为8V。
根据表4也可进一步论证：有机发光器件I和J的EL光谱均呈现出良好的客体FIrpic的发射峰，CIE坐标分别为(0.14,0.30)和(0.15,0.36)，且在不同的电压下保持稳定，这就从结果上证实了这两个材料的三重态激子可以完整地传递给客体材料。而对于pBITP，相较于前面的两个化合物，由于对位相连的两个苯之间形成的共轭程度较大，使得三重态能级只有2.72eV，只是略高于客体FIrpic的三重态能级，不能保证三重态能量的完全转移。从有机发光器件K的EL光谱来看，除去客体FIrpic的发射峰之外，在600nm处还有一肩峰，这说明三重态激子没有实现很好的主客体之间的转移，并且电子空穴的复合区域不在发光层中心，从而进一步引起器件效率很低。
虽然已经参照特定实施例示出并描述了本发明，但是本领域的技术人员将理解：在不脱离由权利要求及其等同物限定的本发明的精神和范围的情况下，可在此进行形式和细节上的各种变化。

Claims (12)

  1. 一种有机发光器件，从下至上包括：衬底、阳极层、空穴注入层、空穴传输层、激子阻隔层、有机发光层、电子传输层、电子注入层和阴极层；其中，所述有机发光层包括式1所示的苯并咪唑衍生物，
    Figure PCTCN2017089607-appb-100001
    其中，P1、P2、P3为苯环，R1～R12中至少一个为具有空穴传输能力的取代基团。
  2. 根据权利要求1所述有机发光器件，其中，所述具有空穴传输能力的取代基团选自碳原子个数为5～65的杂环基团，或者碳原子个数为6～65的芳香基团、多环基团、亚芳香基团或亚芳香杂环基团。
  3. 根据权利要求1所述有机发光器件，其中，所述R1～R12选自氢基、苯基、对甲苯基、二氮杂-9-咔唑基、三苯基硅基、对三苯胺基、二甲基对三苯胺基、二代叔丁基咔唑基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、3，6-二叔丁基咔唑苯基、二代3，6-二叔丁基咔唑苯基、对三苯胺基、二甲基对三苯胺基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、2-二苯并噻吩、3-二苯并噻吩、4-二苯并噻吩、间三联苯基。
  4. 根据权利要求2所述有机发光器件，其中，所述R1～R12选自氢基、苯基、对甲苯基、二氮杂-9-咔唑基、三苯基硅基、对三苯胺基、二甲基对三苯胺基、二代叔丁基咔唑基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、3，6-二叔丁基咔唑苯基、二代3，6-二叔丁基咔唑苯基、对三苯胺基、二甲基对三苯胺基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、2-二苯并噻吩、3-二苯 并噻吩、4-二苯并噻吩、间三联苯基。
  5. 根据权利要求1所述有机发光器件，其中，所述有机发光层还包括掺杂剂，所述掺杂剂为双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱，或者，乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)；所述掺杂剂占所述有机发光层的质量分数为0.5～7wt％。
  6. 根据权利要求5所述有机发光器件，其中，所述掺杂剂乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)占所述有机发光层的质量分数为0.5～2wt％。
  7. 根据权利要求1所述有机发光器件，其中，所述阳极层材质为半导体导电膜；所述空穴注入层材质为氧化钼；所述空穴传输层材质为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺或者4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]；所述激子阻隔层材质为N,N′-二咔唑-3,5-苯或者4,4',4″-三(咔唑-9-基)三苯胺；所述电子传输层的材质为1,3,5-三[(3-吡啶基)-3-苯基]苯；所述电子注入层的材质为LiF；所述阴极层为Al。
  8. 一种有机发光器件的制备方法，其中，包括如下步骤：
    在衬底上形成阳极层；
    采用真空热蒸镀方法，在所述阳极层依次形成空穴注入层、空穴传输层、激子阻隔层，
    采用真空热蒸镀方法，在所述激子阻隔层上形成有机发光层，所述有机发光层材料包括式1所示的苯并咪唑衍生物，
    Figure PCTCN2017089607-appb-100002
    其中，P1、P2、P3为苯环，R1～R12中至少一个为具有空穴传输能力的取代基团；
    再利用真空热蒸镀方法在所述有机发光层上形成电子传输层、电子注入层和阴极层。
  9. 根据权利要求8所述有机发光层的制备方法，其中，所述具有空穴传输能力的取代基团选自碳原子个数为5～65的杂环基团，或者碳原子个数为6～65的芳香基团、多环基团、亚芳香基团或亚芳香杂环基团。
  10. 根据权利要求8所述有机发光器件的制备方法，其中，所述R1～R12选自氢基、苯基、对甲苯基、二氮杂-9-咔唑基、三苯基硅基、对三苯胺基、二甲基对三苯胺基、二代叔丁基咔唑基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、3，6-二叔丁基咔唑苯基、二代3，6-二叔丁基咔唑苯基、对三苯胺基、二甲基对三苯胺基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、2-二苯并噻吩、3-二苯并噻吩、4-二苯并噻吩、间三联苯基。
  11. 根据权利要求9所述有机发光器件的制备方法，其中，所述R1～R12选自氢基、苯基、对甲苯基、二氮杂-9-咔唑基、三苯基硅基、对三苯胺基、二甲基对三苯胺基、二代叔丁基咔唑基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、3，6-二叔丁基咔唑苯基、二代3，6-二叔丁基咔唑苯基、对三苯胺基、二甲基对三苯胺基、1-萘取代对三苯胺基、2-萘取代对三苯胺基、2-二苯并噻吩、3-二苯并噻吩、4-二苯并噻吩、间三联苯基。
  12. 根据权利要求8所述有机发光器件的制备方法，其中，所述有机发光层还包括掺杂剂，所述掺杂剂为双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱，或者，乙酰丙酮酸二(2-苯基苯并噻唑-C2,N)合铱(III)；所述掺杂剂占所述有机发光层的质量分数为0.5～7wt％。
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