WO2019085759A1 - 一种以氮杂螺芴和芳基酮为核心的化合物、其制备方法及其在oled上的应用 - Google Patents

一种以氮杂螺芴和芳基酮为核心的化合物、其制备方法及其在oled上的应用 Download PDF

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WO2019085759A1
WO2019085759A1 PCT/CN2018/110694 CN2018110694W WO2019085759A1 WO 2019085759 A1 WO2019085759 A1 WO 2019085759A1 CN 2018110694 W CN2018110694 W CN 2018110694W WO 2019085759 A1 WO2019085759 A1 WO 2019085759A1
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compound
preparation
aryl ketone
aza
layer
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French (fr)
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吴秀芹
李崇
张兆超
张小庆
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江苏三月光电科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/20—Spiro-condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials 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

Definitions

  • the invention relates to the technical field of semiconductors, in particular to a compound with aza-spiroquinone and an aryl ketone as a core, a preparation method thereof and application thereof to an OLED.
  • OLED Organic Light Emission Diodes
  • the OLED device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED device.
  • As a current device when a voltage is applied to the electrodes of both ends of the OLED light-emitting device, and the positive and negative charges in the film layer of the organic layer functional material are applied by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, OLED electroluminescence is generated.
  • OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as television.
  • OLED devices have luminous efficiency and service life. Further improvement is needed.
  • Research on improving the performance of OLED devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device.
  • the photoelectric functional materials applied to the OLED device can be divided into two categories, namely, charge injection transport materials and luminescent materials, and further, the charge injection transport materials can be divided into electron injection transport materials, electron blocking materials, and hole injection.
  • the transfer material and the hole blocking material may also be divided into a host light emitting material and a dopant material.
  • various organic functional materials are required to have good photoelectric characteristics. For example, as a charge transport material, it is required to have good carrier mobility, high glass transition temperature, etc., as a host material of the light-emitting layer. The material is required to have good bipolarity, appropriate HOMO/LUMO energy levels, and the like.
  • the photoelectric functional material film layer constituting the OLED device includes at least two or more layers, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron transport.
  • a plurality of layers such as a layer and an electron injecting layer, that is, an optoelectronic functional material applied to an OLED device includes at least a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, etc., and the material type and the matching form are rich. And the characteristics of diversity.
  • the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in different structural devices may be completely different. Therefore, in view of the industrial application requirements of current OLED devices, and the different functional film layers of OLED devices, the photoelectric characteristics of the devices must be selected to be more suitable, and high-performance OLED functional materials or material combinations can achieve high efficiency and long device. Comprehensive characteristics of life and low voltage. As far as the actual demand of the current OLED display lighting industry is concerned, the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.
  • the present applicant provides a compound having aza-spiroquinone and an aryl ketone as a core, a preparation method thereof and use thereof in an organic electroluminescence device.
  • the compound of the invention contains aza-spirofluorene structure, has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, high electron mobility, and can effectively improve the luminous efficiency of the device after being fabricated by the OLED device. And the lifetime of OLED devices.
  • One aspect of the present invention provides a compound having aza-spiroquinone and an aryl ketone as a core, and the structure of the compound is as shown in the formula (1):
  • X is independently represented as N or CH, and at least one X is N;
  • L represents one of a single bond, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 5 to C 30 heteroarylene group.
  • X is represented by the number of N being 1, 2 or 4.
  • N is symmetric in the position of the azaindole group.
  • L is represented by one of a phenylene group, a biphenylylene group or a naphthylene group.
  • Another aspect of the invention provides a method of preparing a compound as described above, comprising the steps of:
  • the raw material A is dissolved in tetrahydrofuran, the intermediate A and Pd(PPh 3 ) 4 are added, stirred, and then the K 2 CO 3 solution is added, and the mixed solution of the above reactants is heated and refluxed at 80 ° C. -20h, after the reaction was completed, the water was added to the mixed solution, and the mixture was extracted with methylene chloride. The extract was dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure. ;
  • reaction equation that occurs during the preparation of intermediate A is as follows:
  • the present invention also provides the use of a compound having aza-spiroquinone and an aryl ketone as a core as described above for the preparation of an organic electroluminescent device.
  • the present invention also provides an organic electroluminescent device comprising at least one functional layer, the functional layer comprising a compound having azacrostine and an aryl ketone as a core as described above.
  • the present invention also provides an organic electroluminescent device comprising a hole blocking layer/electron transporting layer, the material for which the hole blocking layer/electron transporting layer contains azacrostine and aryl ketone as described above The core compound.
  • the present invention also provides an organic electroluminescent device comprising a light-emitting layer comprising a compound having azacrostine and an aryl ketone as a core as described above.
  • the invention also provides an illumination or display element comprising an organic electroluminescent device as described above.
  • the compound of the present invention has azaphthoquinone and aryl ketone as skeletons, and azaspiro and aryl ketones are strong electron groups, have deep HOMO levels and high electron mobility, and are modified by other aromatic groups.
  • the HOMO level can be adjusted freely, and can be used as an electronic luminescent material or as a hole blocking or electron transport layer material.
  • the structure of the present invention containing a hole group can balance the electrons and holes of the material, so that the material can be used as a host material of the electron-emitting type light-emitting layer.
  • the number and position of N in the azaindole group affect the HOMO level and LUMO level of the material and the triplet level distribution.
  • the HOMO level can be used as a hole blocking or electron transport layer material.
  • HOMO energy A lighter grade material can be used as the host material of the electron-emitting type of the electron-emitting layer.
  • the azaindole moiety and the aryl ketone are strong electron withdrawing groups, which are separated by a conjugated ⁇ bond, which destroys the molecular symmetry and avoids the aggregation between molecules.
  • the compound of the present invention has a strong rigidity and has an intermolecular relationship. It is difficult to crystallize, is not easy to aggregate, has good film forming properties, and has high glass transition temperature and thermal stability. Therefore, when the compound of the present invention is applied to an OLED device, the film stability after film formation can be maintained, and the OLED can be improved. Device lifetime.
  • the compound of the invention is applied as an organic electroluminescent functional layer material to an OLED device, the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the device lifetime is greatly improved, in the OLED light-emitting device. It has good application effect and has good industrialization prospects.
  • 1 is a schematic view showing the structure of a compound of the present invention applied to an OLED device
  • FIG. 2 is a graph showing the current efficiency of an OLED device prepared from a compound of the present invention measured at different temperatures.
  • the reagents, materials, and instruments used are all conventional reagents, conventional materials, and conventional instruments, unless otherwise specified, and are commercially available, and the reagents involved may also be conventionally used. Synthetic methods are obtained synthetically.
  • the specific preparation examples of the intermediate A are described below by the embodiment 1.
  • the naming of the intermediate A of each example can be distinguished by an Arabic numeral, such as the intermediate A1, the intermediate A2 and the like.
  • the preparation method of the other intermediate A is similar to that of the intermediate A1, and the specific structural formula of the intermediate A used in the present invention is shown in Table 1.
  • the preparation process was as follows: in a 250 mL three-necked flask, nitrogen gas was introduced, 0.01 mol of raw material 1, 150 mL of THF, 0.015 mol of intermediate A1, 0.0001 mol of Pd(PPh 3 ) 4 , stirred, and then 10 mL of 2 M K 2 CO were added. 3 aqueous solution, heated to 80 ° C, reflux reaction for 15h, sampling the plate, the reaction is complete. The mixture was cooled with EtOAc (EtOAc) (EtOAc).
  • Elemental analysis structure (Molecular formula C 42 H 24 N 2 O 2 ): Theory C, 85.70; H, 4.11; N, 4.76; O, 5.44; Tests: C, 85.70; H, 4.12; N, 4.75; 5.44.
  • ESI-MS (m/z) (M + ): Theory: 588.
  • Compound 8 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 2 and the intermediate A1 was replaced with the intermediate A2.
  • Elemental analysis structure (Molecular formula C 42 H 24 N 2 O 2 ): Theory: C, 85.70; H, 4.11; N, 4.76; O, 5.44; Test value: C, 85.71; H, 4.10; N, 4.76; , 5.44.
  • Compound 12 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 3 and the intermediate A1 was replaced with the intermediate A3.
  • Elemental analysis structure (Molecular formula C 42 H 24 N 2 O 2 ): Theory C, 85.70; H, 4.11; N, 4.76; O, 5.44; Tests: C, 85.69; H, 4.12; N, 4.77; 5.43.
  • Compound 22 was prepared in the same manner as in Example 2-3 except that Intermediate A3 was replaced with Intermediate A4.
  • Elemental analysis structure (Molecular formula C 42 H 24 N 2 OS): Theory C, 83.42; H, 4.40; N, 4.63; O, 2.65; S, 5.30; Test value: C, 83.43; H, 4.00; N, 4.64 ;O, 2.64; S, 5.31.
  • Compound 41 was prepared in the same manner as in Example 2-1 except that Intermediate A1 was replaced with Intermediate A6.
  • Elemental analysis structure (Molecular formula C 48 H 28 N 2 O 2 ): Theory C, 86.73; H, 4.25; N, 4.21.; O, 4.81; Tests: C, 86.72; H, 4.25; N, 4.21; 4.82.
  • ESI-MS (m/z) (M + ): calc.
  • Compound 50 was prepared in the same manner as in Example 2-2 except that Intermediate A2 was replaced with Intermediate A7.
  • Elemental analysis structure (Molecular formula C 48 H 28 N 2 O 2 ): Theory C, 86.73; H, 4.25; N, 4.21.; O, 4.81; Tests: C, 86.72; H, 4.25; N, 4.22; 4.81.
  • ESI-MS (m/z) (M + ): calc.
  • Elemental analysis structure (Molecular formula C 48 H 28 N 2 O 2 ): Theory: C, 86.73; H, 4.25; N, 4.21.; O, 4.81; Test value: C, 86.72; H, 4.25; N, 4.22; , 4.81.
  • ESI-MS (m/z) (M + ): calc.
  • Elemental analysis structure (Molecular formula C 46 H 26 N 2 O 2 ): Theory C, 86.50; H, 4.10; N, 4.39; O, 5.01; Test: C, 86.51; H, 4.10; N, 4.39; 5.00.
  • Compound 80 was prepared in the same manner as in Example 2-1 except that Intermediate A10 was used to replace Intermediate A1.
  • Elemental analysis structure (Molecular formula C 46 H 26 N 2 O 2 ): Theory C, 86.50; H, 4.10; N, 4.39; O, 5.01; C, 86.51; H, 4.10; N, 4.38; O, 5.01 .
  • Compound 91 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 4.
  • Elemental analysis structure (Molecular formula C 43 H 25 NO 2 ): calcd. C, 87.88; H, 4.29; N, 2.38; O, 5.44; Tests: C, 87.88; H, 4.28; N, 2.38; O, 5.44.
  • ESI-MS (m/z) (M + ): 553.68.
  • Compound 99 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 5 and the intermediate A1 was replaced with the intermediate A12.
  • Compound 112 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 6, and the intermediate A1 was replaced with the intermediate A11.
  • Compound 128 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 7 and the intermediate A1 was replaced with the intermediate A7.
  • Elemental analysis structure (Molecular formula C 49 H 29 NO 2 ): calcd. C, 88.67; H, 4.40; N, 2.11; O, 4.82; Tests: C, 88.67; H, 4.40; N, 2.10; O, 4.81.
  • ESI-MS m/z (M + ): calc. 663.78.
  • Compound 137 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 8 and the intermediate A1 was replaced with the intermediate A8.
  • Compound 150 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 9.
  • Elemental analysis structure (Molecular formula C 40 H 22 N 4 O 2 ): Theory C, 81.34; H, 3.75; N, 9.49; O, 5.42; Tests: C, 81.35; H, 3.75; N, 9.48; 5.42.
  • ESI-MS (m/z) (M + ): 550.64.
  • Compound 162 was prepared in the same manner as in Example 2-1 except that the starting material 1 was replaced with the starting material 3 and the intermediate A1 was replaced with the intermediate A13.
  • the compound of the invention is used in a light-emitting device, has a high glass transition temperature (Tg) and a triplet energy level (T 1 ), a suitable HOMO, LUMO energy level, can be used as a hole blocking/electron transport material, or as a The luminescent layer material is used.
  • Tg glass transition temperature
  • T 1 triplet energy level
  • HOMO HOMO
  • LUMO LUMO energy level
  • the triplet energy level T1 is tested by Hitachi's F4600 fluorescence spectrometer.
  • the test conditions of the material are 2*10 -5 toluene solution;
  • the glass transition temperature Tg is by differential scanning calorimetry (DSC, Germany Benz DSC204F1 differential scanning) The calorimeter was measured at a heating rate of 10 ° C/min;
  • the thermogravimetric temperature Td was a temperature at which the weight loss was 1% in a nitrogen atmosphere, and was measured on a TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, and the flow rate of nitrogen was 20 mL/ Min;
  • the highest occupied molecular orbital HOMO level is tested by the ionization energy test system (IPS3) and tested as the atmospheric environment.
  • IPS3 ionization energy test system
  • the compound of the invention has high glass transition temperature, can improve the phase stability of the material film, further improve the service life of the device; has a high triplet energy level, can block the energy loss of the light-emitting layer, thereby improving the device.
  • Luminous efficiency At the same time, the material of the invention has a suitable HOMO energy level to solve the carrier injection problem, and the device voltage can be reduced; therefore, the compound with the aza-spiro- fluorene and the aryl ketone as the core is applied to different functional layers of the OLED device. It can effectively improve the luminous efficiency and service life of the device.
  • Example 3 The application effect of the compound of the present invention in an OLED device will be described in detail below by way of Example 3.
  • the fabrication process of the device was identical, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept the same, except that Example 3-1
  • the composition of the light-emitting layer in the device was changed to Examples 3-8; the material of the hole blocking/electron transport layer of the device was changed in Examples 3-9 to 3-18, and the performance of the device obtained in each example
  • the test results are shown in Table 3.
  • an electroluminescent device is prepared as follows:
  • HAT-CN is deposited as a hole injection layer 3 by vacuum evaporation, and the thickness of evaporation is 10 nm;
  • a cathode Al was vacuum-deposited as a cathode reflective electrode layer 8, and a thickness of 100 nm was evaporated; and the device 1 was obtained.
  • This embodiment is different from Embodiment 3-1 in that the luminescent layer host material of the OLED device is Compound 8.
  • This embodiment differs from Example 3-1 in that the luminescent layer host material of the OLED device is compound 12, and the mass ratio of compound 12 to Ir(ppy) 3 is 92:8.
  • This embodiment is different from Example 3-1 in that the luminescent layer host material of the OLED device is compound 22, and the mass ratio of compound 22 to Ir(ppy) 3 is 88:12.
  • This embodiment differs from Example 3-1 in that the luminescent layer host material of the OLED device is compound 34 and compound GH, and the mass ratio of compound 34, GH, and Ir(ppy) 3 is 60:30:10.
  • This embodiment differs from Example 3-1 in that the luminescent layer host material of the OLED device is compound 91 and compound GH, and the mass ratio of compound 91, GH, and Ir(ppy) 3 is 60:30:10.
  • This embodiment differs from Example 3-1 in that the luminescent layer host material of the OLED device is compound 99 and compound GH, and the mass ratio of compound 99, GH, and Ir(ppy) 3 is 60:30:10.
  • the luminescent layer host material of the OLED device is the compound 112 and the compound GH, and the compound 112, GH and Ir(ppy) 3 have a mass ratio of 60:30:10.
  • Embodiment 3-1 differs from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 41, and the mass ratio of CBP to Ir(ppy) 3 is 88: 12.
  • This embodiment is different from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 50, and the mass ratio of CBP to Ir(ppy) 3 is 90: 10.
  • the luminescent layer body material of the OLED device is CBP
  • the hole blocking/electron transport layer material is compound 59
  • the mass ratio of CBP and Ir(ppy) 3 is 80: 20.
  • Embodiment 3-1 differs from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 68, and the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • Embodiment 3-1 differs from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 80, and the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • the luminescent layer body material of the OLED device is CBP
  • the hole blocking/electron transport layer material is compound 80
  • the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • Embodiment 3-1 differs from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 128, and the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • This embodiment differs from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 137, and the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • Embodiment 3-1 differs from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 150, and the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • the luminescent layer body material of the OLED device is CBP
  • the hole blocking/electron transport layer material is compound 150
  • the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • This embodiment is different from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 162, and the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • This embodiment is different from Embodiment 3-1 in that the luminescent layer body material of the OLED device is CBP, the hole blocking/electron transport layer material is compound 162, and the mass ratio of CBP to Ir(ppy) 3 is 80: 20.
  • the comparative example is different from Example 3-1 in that the luminescent layer host material of the OLED device is CBP, and the hole blocking/electron transport layer material is TPBI.
  • the life test system is the OLED device life tester jointly researched by the owner of the invention and Shanghai University.
  • the OLED device prepared by the compound of the invention has relatively stable efficiency when working at low temperature, and the efficiency is tested in the range of -10 to 80 °C of the devices 1, 5, 11 and the device, and the results are shown in Table 4 and Figure 2. :
  • the devices 1, 6, and 12 are the device structures of the materials of the present invention and the known materials, and the low-temperature efficiency is higher than that of the device comparative examples, and the efficiency is increased during the temperature increase. Smoothly rise.

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Abstract

本发明涉及一种以氮杂螺芴和芳基酮为核心的化合物、其制备方法及其在OLED上的应用，该化合物含有氮杂螺芴和芳基酮结构，且螺芴结构上至少有一个N；氮杂螺芴和芳基酮基团都是强电子基团，具有深的HOMO能级和高电子迁移率，适合作为空穴阻挡材料或电子传输材料应用；本发明含有空穴基团的结构，可平衡材料的电子和空穴，使得材料可作为偏电子型发光层主体材料使用；另外，本发明化合物基团刚性较强，具有分子间不易结晶、不易聚集、具有良好成膜性的特点。作为有机电致发光功能层材料应用于OLED器件后，器件的电流效率，功率效率和外量子效率均得到很大改善；同时，对于器件寿命提升非常明显。

Description

一种以氮杂螺芴和芳基酮为核心的化合物、其制备方法及其在OLED上的应用 技术领域
本发明涉及半导体技术领域，具体涉及一种以氮杂螺芴和芳基酮为核心的化合物、其制备方法及其在OLED上的应用。
背景技术
有机电致发光(Organic Light Emission Diodes，OLED)器件技术既可以用来制造新型显示产品，也可以用于制作新型照明产品，有望替代现有的液晶显示和荧光灯照明，应用前景十分广泛。OLED器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成OLED器件。作为电流器件，当对OLED发光器件的两端电极施加电压，并通过电场作用有机层功能材料膜层中的正负电荷，正负电荷进一步在发光层中复合，即产生OLED电致发光。
当前，OLED显示技术已经在智能手机、平板电脑等领域获得应用，进一步还将向电视等大尺寸应用领域扩展，但是，和实际的产品应用要求相比，OLED器件的发光效率，使用寿命等性能还需要进一步提升。对于OLED器件提高性能的研究包括：降低器件的驱动电压，提高器件的发光效率，提高器件的使用寿命等。为了实现OLED器件的性能的不断提升，不但需要从OLED器件结构和制作工艺的创新，更需要OLED光电功能材料不断研究和创新，创制出更高性能OLED的功能材料。应用于OLED器件的光电功能材料从用途上可划分为两大类，即电荷注入传输材料和发光材料，进一步，还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料，还可以将发光材料分为主体发光材料和掺杂材料。为了制作高性能的OLED器件，要求各种有机功能材料具备良好的光电特性，譬如，作为电荷传输材料，要求具有良好的载流子迁移率，高玻璃化转化温度等，作为发光层的主体材料要求材料具有良好双极性，适当的HOMO/LUMO能阶等。
构成OLED器件的光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构，则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层，也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料，空穴传输材料，发光材料，电子传输材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同的材料在不同结构器件中的性能表现，也可能完全迥异。因此，针对当前OLED器件的产业应用要求，以及OLED器件的不同功能膜层，器件的光电 特性需求，必须选择更适合，具有高性能的OLED功能材料或材料组合，才能实现器件的高效率、长寿命和低电压的综合特性。就当前OLED显示照明产业的实际需求而言，目前OLED材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有技术存在的上述问题，本申请人提供了一种以氮杂螺芴和芳基酮为核心的化合物、其制备方法及其在有机电致发光器件上的应用。本发明化合物含有氮杂螺芴结构，具有较高的玻璃化温度和分子热稳定性，合适的HOMO和LUMO能级，高电子迁移率，应用于OLED器件制作后，可有效提高器件的发光效率和OLED器件的使用寿命。
本发明的技术方案如下：
本发明一方面提供了一种以氮杂螺芴和芳基酮为核心的化合物，该化合物的结构如通式(1)所示：
Figure PCTCN2018110694-appb-000001
其中，X独立的表示为N或CH，且至少一个X为N；
Z表示为O、S、C 1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基中的一种，i等于0或1；其中当i＝0时，芳基酮表示为如下结构式：
Figure PCTCN2018110694-appb-000002
L表示为单键、经取代或未经取代的C 6至C 30亚芳基、经取代或未经取代的C 5至C 30亚杂芳基中的一种。
进一步的，通式(1)中，X表示为N的数量为1、2或4。
进一步的，当X表示为N的数量为2或4时，N在氮杂螺芴基团中所处的位置对称。
进一步的，L表示为亚苯基、亚联苯基或亚萘基中的一种。
进一步的，所述化合物的具体结构式为以下任意一种：
Figure PCTCN2018110694-appb-000003
Figure PCTCN2018110694-appb-000004
Figure PCTCN2018110694-appb-000005
Figure PCTCN2018110694-appb-000006
Figure PCTCN2018110694-appb-000007
Figure PCTCN2018110694-appb-000008
Figure PCTCN2018110694-appb-000009
Figure PCTCN2018110694-appb-000010
Figure PCTCN2018110694-appb-000011
Figure PCTCN2018110694-appb-000012
本发明另一方面提供了一种如上所述的化合物的制备方法，包括如下步骤：
在惰性气体保护下，将原料A溶解于四氢呋喃中，加入中间体A和Pd(PPh 3) 4，搅拌，再加入K 2CO 3溶液，将上述反应物的混合溶液于80℃下加热回流5-20h，反应结束后，在上述混合溶液中冷却加水，用二氯甲烷萃取，萃取液用无水硫酸钠干燥，过滤，得到的滤液减压浓缩，所得残余物过硅胶柱纯化，得到目标化合物；
制备过程中发生的反应方程式如下：
Figure PCTCN2018110694-appb-000013
进一步的，原料A与中间体A的摩尔比为原料A：中间体A＝1:1.0-1.5；Pd(PPh 3) 4与原料A的摩尔比为Pd(PPh 3) 4：原料A＝0.001-0.02:1；K 2CO 3与原料A的摩尔比为K 2CO 3：原料A＝1.0-2.0:1；THF与原料A的用量比为1g原料A加入10-30ml THF。
进一步的，中间体A的制备步骤如下：
S1：在惰性气体保护下，将原料B溶解于四氢呋喃中，加入原料C和Pd(PPh 3) 4，搅拌，再加入2M的K 2CO 3溶液，将上述反应物的混合溶液于80℃下加热回流5-20h。反应结束后，冷却加水，用二氯甲烷萃取，萃取液用无水硫酸钠干燥，过滤，得到的滤液减压浓缩，浓缩残余物过硅胶柱纯化，得到中间体I；
S2：在惰性气体保护下，将中间体I溶解于四氢呋喃中，加入双(频哪醇根基)二硼、Pd(dppf) 2Cl 2和K(acac)，搅拌，将上述反应物的混合溶液于80℃下加热回流5-10h；反应结束后，加水冷却、将所得溶液过滤并在真空烘箱中干燥，干燥残余物过硅胶柱纯化，得到中间体A；
中间体A的制备过程中发生的反应方程式如下：
Figure PCTCN2018110694-appb-000014
进一步的，原料B与原料C的摩尔比为原料B：原料C＝1:1.0-1.5；Pd(PPh 3) 4与原料B的摩尔比为Pd(PPh 3) 4：原料B＝0.001-0.02:1；K 2CO 3与原料B的摩尔比为K 2CO 3：原料B＝1.0-2.0:1；中间体I与双(频哪醇根基)二硼的摩尔比为中间体I：双(频哪醇根基)二硼＝1:1.0-1.5；Pd(dppf) 2Cl 2与中间体I的摩尔比为Pd(dppf) 2Cl 2：中间体I＝0.001-0.02:1；K 2CO 3与中间体I的摩尔比为K 2CO 3：中间体I＝1.0-2.5:1。
本发明还提供了如上所述的以氮杂螺芴和芳基酮为核心的化合物在制备有机电致发光器件中的应用。
本发明还提供了一种有机电致发光器件，包括至少一层功能层，所述功能层所用材料含有如上所述的以氮杂螺芴和芳基酮为核心的化合物。
本发明还提供了一种有机电致发光器件，包括空穴阻挡层/电子传输层，所述空穴阻挡层/电子传输层所用材料含有如上所述的以氮杂螺芴和芳基酮为核心的化合物。
本发明还提供了一种有机电致发光器件，包括发光层，所述发光层所用材料含有如上所述的以氮杂螺芴和芳基酮为核心的化合物。
本发明还提供了一种照明或显示元件，包括如上所述的有机电致发光器件。
本发明的有益技术效果在于：
本发明化合物以氮杂螺芴和芳基酮为骨架，氮杂螺芴和芳基酮均为强电子性基团，具有深的HOMO能级和高电子迁移率，通过其他芳香基团的修饰，使HOMO能级自由调整，可以作为电子型发光材料使用，也可以作为空穴阻挡或电子传输层材料使用。本发明含有空穴基团的结构，可平衡材料的电子和空穴，使得材料可作为偏电子型发光层主体材料使用。氮杂螺芴基团中N的数量和位置会影响材料的HOMO能级和LUMO能级以及三线态能级分布，HOMO能级较深的材料可作为空穴阻挡或电子传输层材料，HOMO能级较浅的材料可作为偏电子型的发光层主体材料使用。
另外，氮杂芴部分和芳基酮都是强吸电子基团，中间以共轭π键相隔，破坏分子对称性，避免分子间的聚集作用，本发明化合物基团刚性较强，具有分子间不易结晶、不易聚集、具有良好成膜性的特点，具有高的玻璃化温度及热稳定性，所以，本发明化合物应用于OLED器件时，可保持材料成膜后的膜层稳定性，提高OLED器件使用寿命。本发明所述化合物作为有机电致发光功能层材料应用于OLED器件后，器件的电流效率，功率效率和外量子效率均得到很大改善；同时，对于器件寿命提升非常明显，在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
附图说明
图1为本发明的化合物应用于OLED器件的结构示意图；
图2为本发明的化合物制备的OLED器件在不同温度下测量的电流效率曲线图。
附图标记说明：1—透明基板层；2—ITO阳极层；3—空穴注入层，4—空穴传输或电子阻挡层；5—发光层；6—电子传输或空穴阻挡层；7—电子注入层；8—阴极反射电极层。
具体实施方式
以下将结合实施例和附图来详细说明本发明的实施方式，所举实施例只用于解释本发明，并非用于限定本发明的范围。
在下述实施例、对比例中，所使用到的试剂、材料以及仪器如没有特殊的说明，均为常规试剂、常规材料以及常规仪器，均可商购获得，其中所涉及的试剂也可通过常规合成方法合成获得。
下面通过实施例1描述中间体A的具体制备实例，各实例的中间体A的命名可用阿拉伯数字加以区分，比如中间体A1，中间体A2等。
实施例1中间体A的制备
实施例1-1中间体A1的制备
Figure PCTCN2018110694-appb-000015
S1：在250mL三口瓶中，通入氮气，加入0.02mol原料B1，150ml的THF，0.025mol原料C1，0.0002mol Pd(PPh 3) 4，搅拌，然后加入15ml,2M的K 2CO 3水溶液，加热至80℃，回流反应10h，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到中间体I1；中间体I1的HPLC纯度99.0％，收率73.1％；元素分析结构(分子式C 19H 11ClO 2)：理论值C,74.40；H,3.61；Cl,11.56；O,10.43；测试值：C,74.41；H,3.60；Cl,11.55；N,10.44；ESI-MS(m/z)(M +)：理论值为306.75，实测值为306.19；
Figure PCTCN2018110694-appb-000016
S2：在250mL三口瓶中，通入氮气，加入0.02mol中间体I1溶解于150ml四氢呋喃中，再将0.024mol双(频哪醇根基)二硼、0.0002mol Pd(dppf) 2Cl 2以及0.05mol乙酸钾加入，搅拌混合物，将上述反应物的混合溶液于80℃下加热回流5h；反应结束后，冷却并加入100ml水、且将混合物过滤并在真空烘箱中干燥。将所获得的残余物过硅胶柱分离纯化，得到中间体A1；中间体A1的HPLC纯度99.5％，收率90.8％；元素分析结构(分子式C 25H 23BO 4)：理论值C,75.40；H,5.82；B,2.71；O,16.07；测试值：C,75.40；H,5.83；B,2.71；O,16.06；ESI-MS(m/z)(M +)：理论值为398.26，实测值为398.10。
其他中间体A的制备方法与中间体A1相似，本发明所用到的中间体A的具体结构式如表1所示。
表1
Figure PCTCN2018110694-appb-000017
Figure PCTCN2018110694-appb-000018
Figure PCTCN2018110694-appb-000019
实施例2以氮杂螺芴和芳基酮为核心的化合物的制备
实施例2-1化合物1的制备
Figure PCTCN2018110694-appb-000020
制备过程如下：在250mL三口瓶中，通入氮气，加入0.01mol原料1，150mL的THF，0.015mol中间体A1，0.0001mol Pd(PPh 3) 4，搅拌，然后加入10mL,2M的K 2CO 3水溶液，加热至80℃，回流反应15h，取样点板，反应完全。自然冷却，用200mL二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到目标化合物，HPLC纯度99.0％，收率78.5％。
元素分析结构(分子式C 42H 24N 2O 2)：理论值C,85.70；H,4.11；N,4.76；O,5.44；测试值：C,85.70；H,4.12；N,4.75；O,5.44。ESI-MS(m/z)(M +)：理论值为588.67，实测值为588.51。
实施例2-2化合物8的制备
Figure PCTCN2018110694-appb-000021
化合物8的制备方法同实施例2-1，不同之处在于用原料2替换原料1，用中间体A2替换中间体A1。
元素分析结构(分子式C 42H 24N 2O 2)：理论值:C,85.70；H,4.11；N,4.76；O,5.44；测试值：C,85.71；H,4.10；N,4.76；O,5.44。ESI-MS(m/z)(M +)：理论值为588.18，实测值为588.08。
实施例2-3化合物12的制备
Figure PCTCN2018110694-appb-000022
化合物12的制备方法同实施例2-1，不同之处在于用原料3替换原料1，用中间体A3替换中间体A1。
元素分析结构(分子式C 42H 24N 2O 2)：理论值C,85.70；H,4.11；N,4.76；O,5.44；测试值：C,85.69；H,4.12；N,4.77；O,5.43。ESI-MS(m/z)(M +)：理论值为588.67，实测值为588.51。
实施例2-4化合物22的制备：
Figure PCTCN2018110694-appb-000023
化合物22的制备方法同实施例2-3，不同之处在于用中间体A4替换中间体A3。
元素分析结构(分子式C 42H 24N 2OS)：理论值C,83.42；H,4.00；N,4.63；O,2.65；S,5.30；测试值：C,83.43；H,4.00；N,4.64；O,2.64；S,5.31。ESI-MS(m/z)(M +)：理论值为604.73，实测值为604.29。
实施例2-5化合物34的制备
Figure PCTCN2018110694-appb-000024
化合物34的制备方法同实施例2-1，不同之处在于用中间体A5替换中间体A1。
元素分析结构(分子式C 48H 29N 3O)：理论值C,86.86；H,4.40；N,6.33；O,2.41；测试值：C,86.85；H,4.40；N,6.34；O,2.41。ESI-MS(m/z)(M +)：理论值为663.78，实测值为663.16。
实施例2-6化合物41的制备
Figure PCTCN2018110694-appb-000025
化合物41的制备方法同实施例2-1，不同之处在于用中间体A6替换中间体A1。
元素分析结构(分子式C 48H 28N 2O 2)：理论值C,86.73；H,4.25；N,4.21；O,4.81；测试值：C,86.72；H,4.25；N,4.21；O,4.82。ESI-MS(m/z)(M +)：理论值为664.76，实测值为664.64。
实施例2-7化合物50的制备
Figure PCTCN2018110694-appb-000026
化合物50的制备方法同实施例2-2，不同之处在于用中间体A7替换中间体A2。
元素分析结构(分子式C 48H 28N 2O 2)：理论值C,86.73；H,4.25；N,4.21；O,4.81；测试值：C,86.72；H,4.25；N,4.22；O,4.81。ESI-MS(m/z)(M +)：理论值为664.76，实测值为664.57。
实施例2-8化合物59的制备
Figure PCTCN2018110694-appb-000027
化合物59的制备方法同实施例2-3，不同之处在于用中间体A8替换中间体A3。
元素分析结构(分子式C 48H 28N 2O 2)：理论值:C,86.73；H,4.25；N,4.21；O,4.81；测试值：C,86.72；H,4.25；N,4.22；O,4.81。ESI-MS(m/z)(M +)：理论值为664.76，实测值为664.81。
实施例2-9化合物68的制备
Figure PCTCN2018110694-appb-000028
化合物68的制备方法同实施例2-2，不同之处在于用中间体A9替换中间体A2。
元素分析结构(分子式C 46H 26N 2O 2)：理论值C,86.50；H,4.10；N,4.39；O,5.01；测试值：C,86.51；H,4.10；N,4.39；O,5.00。ESI-MS(m/z)(M +)：理论值为638.73，实测值为638.49。
实施例2-10化合物80的制备
Figure PCTCN2018110694-appb-000029
化合物80的制备方法同实施例2-1，不同之处在于用中间体A10替换中间 体A1。
元素分析结构(分子式C 46H 26N 2O 2)：理论值C,86.50；H,4.10；N,4.39；O,5.01；测试值C,86.51；H,4.10；N,4.38；O,5.01。ESI-MS(m/z)(M +)：理论值为638.73，实测值为638.80。
实施例2-11化合物91的制备
Figure PCTCN2018110694-appb-000030
化合物91的制备方法同实施例2-1，不同之处在于用原料4替换原料1。
元素分析结构(分子式C 43H 25NO 2)：理论值C,87.88；H,4.29；N,2.38；O,5.44；测试值：C,87.88；H,4.28；N,2.38；O,5.44。ESI-MS(m/z)(M +)：理论值为587.68，实测值为587.71。
实施例2-12化合物99的制备
Figure PCTCN2018110694-appb-000031
化合物99的制备方法同实施例2-1，不同之处在于用原料5替换原料1，用中间体A12替换中间体A1。
元素分析结构(分子式C 46H 31NO)：理论值C,90.02；H,5.09；N,2.28；O,2.61；测试值：C,90.01；H,5.09；N,2.29；O,2.61。ESI-MS(m/z)(M+)：理论值613.76，实测值为613.50。
实施例2-13化合物112的制备
Figure PCTCN2018110694-appb-000032
化合物112的制备方法同实施例2-1，不同之处在于用原料6替换原料1，用中间体A11替换中间体A1。
元素分析结构(分子式C 49H 30N 2O)：理论值C,88.80；H,4.56；N,4.23；O,2.41；测试值：C,88.80；H,4.55；N,4.22；O,2.42。ESI-MS(m/z)(M +)：理论值662.79，实测值为662.61。
实施例2-14化合物128的制备
Figure PCTCN2018110694-appb-000033
化合物128的制备方法同实施例2-1，不同之处在于用原料7替换原料1，用中间体A7替换中间体A1。
元素分析结构(分子式C 49H 29NO 2)：理论值C,88.67；H,4.40；N,2.11；O,4.82；测试值：C,88.67；H,4.40；N,2.10；O,4.81。ESI-MS(m/z)(M +)：理论值为663.78，实测值为663.55。
实施例2-15化合物137的制备
Figure PCTCN2018110694-appb-000034
化合物137的制备方法同实施例2-1，不同之处在于用原料8替换原料1，用中间体A8替换中间体A1。
元素分析结构(分子式C49H 29NO 2)：理论值C,88.67；H,4.40；N,2.11；O,4.82；测试值：C,88.67；H,4.39；N,2.12；O,4.82。ESI-MS(m/z)(M +)：理论值663.78，实测值为663.61。
实施例2-16化合物150的制备
Figure PCTCN2018110694-appb-000035
化合物150的制备方法同实施例2-1，不同之处在于用原料9替换原料1。
元素分析结构(分子式C 40H 22N 4O 2)：理论值C,81.34；H,3.75；N,9.49；O,5.42；测试值：C,81.35；H,3.75；N,9.48；O,5.42。ESI-MS(m/z)(M +)：理论值590.64，实测值为590.52。
实施例2-17化合物162的制备
Figure PCTCN2018110694-appb-000036
化合物162的制备方法同实施例2-1，不同之处在于用原料3替换原料1， 用中间体A13替换中间体A1。
元素分析结构(分子式C 42H 26N 2O)：理论值C,87.78；H,4.56；N,4.87；O,2.78；测试值：C,87.77；H,4.57；N,4.86；O,2.79。ESI-MS(m/z)(M +)：理论值574.68，实测值为574.80。
本发明化合物在发光器件中使用，具有高的玻璃转化温度(Tg)和三线态能级(T 1)，合适的HOMO、LUMO能级，可作为空穴阻挡/电子传输材料使用，也可作为发光层材料使用。对本发明上述实施例制备的化合物分别进行热性能、T 1能级以及HOMO能级测试，结果如表2所示。
表2
Figure PCTCN2018110694-appb-000037
注：三线态能级T1是由日立的F4600荧光光谱仪测试，材料的测试条件为2*10 -5的甲苯溶液；玻璃化温度Tg由示差扫描量热法(DSC，德国耐驰公司DSC204F1示差扫描量热仪)测定，升温速率10℃/min；热失重温度Td是在氮气气氛中失重1％的温度，在日本岛津公司的TGA-50H热重分析仪上进行测定，氮气流量为20mL/min；最高占据分子轨道HOMO能级是由电离能量测试系统(IPS3)测试，测试为大气环境。
由上表数据可知，本发明的化合物具有高的玻璃转化温度，可提高材料 膜相态稳定性，进一步提高器件使用寿命；具有高的三线态能级，可以阻挡发光层能量损失，从而提升器件发光效率。同时本发明材料具有合适的HOMO能级可以解决载流子的注入问题，可降低器件电压；因此，本发明以氮杂螺芴和芳基酮为核心的化合物应用于OLED器件的不同功能层后，可有效提高器件的发光效率及使用寿命。
下面将通过实施例3详细说明本发明的化合物在OLED器件中的应用效果。实施例3所包含的各实施例和对比例中，器件的制作工艺完全相同，并且采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是实施例3-1至实施例3-8对器件中的发光层材料做了变换；实施例3-9至实施例3-18对器件的空穴阻挡/电子传输层材料做了变换，各实施例所得器件的性能测试结果如表3所示。
实施例3OLED器件的制备
实施例3-1：器件1的制备
如图1所示，一种电致发光器件，其制备步骤如下：
a)清洗透明基板层1上的ITO阳极层2(膜后为150nm)，分别用去离子水、丙酮、乙醇超声清洗各15分钟，然后在等离子体清洗器中处理2分钟；
b)在清洗后的ITO阳极层2上，通过真空蒸镀方式蒸镀HAT-CN作为空穴注入层3，蒸镀厚度为10nm；
c)在空穴注入层3上，通过真空蒸镀方式蒸镀NPB作为空穴传输层/电子阻挡层4，蒸镀厚度为80nm；
d)在空穴传输/电子阻挡层4之上蒸镀发光层5，发光层5使用本发明化合物1作为主体材料，Ir(ppy) 3作为掺杂材料，Ir(ppy) 3和化合物1的质量比为1:9，发光层5的蒸镀厚度为30nm；
e)在发光层5之上，通过真空蒸镀方式蒸镀TPBI作为空穴阻挡/电子传输层6，蒸镀厚度为40nm；
f)在空穴阻挡/电子传输层6之上，通过真空蒸镀方式蒸镀LiF作为电子注入层7，蒸镀厚度为1nm；
g)在电子注入层7之上，真空蒸镀阴极Al作为阴极反射电极层8，蒸镀厚度为100nm；得到器件1。
实施例3中用到的材料结构式如下：
Figure PCTCN2018110694-appb-000038
Figure PCTCN2018110694-appb-000039
实施例3-2：器件2的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为化合物8。
实施例3-3：器件3的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为化合物12，化合物12和Ir(ppy) 3的质量比为92:8。
实施例3-4：器件4的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为化合物22，化合物22和Ir(ppy) 3的质量比为88:12。
实施例3-5：器件5的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为化合物34和化合物GH，化合物34、GH和Ir(ppy) 3三者质量比为60:30:10。
实施例3-6：器件6的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为化合物91和化合物GH，化合物91、GH和Ir(ppy) 3三者质量比为60:30:10。
实施例3-7：器件7的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为化合物99和化合物GH，化合物99、GH和Ir(ppy) 3三者质量比为60:30:10。
实施例3-8：器件8的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为化合物112和化合物GH，化合物112、GH和Ir(ppy) 3三者质量比为60:30:10。
实施例3-9：器件9的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物41，CBP和Ir(ppy) 3的质量比为88:12。
实施例3-10：器件10的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物50，CBP和Ir(ppy) 3的质量比为90:10。
实施例3-11：器件11的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物59，CBP和Ir(ppy) 3的质量比为80:20。
实施例3-12：器件12的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物68，CBP和Ir(ppy) 3的质量比为80:20。
实施例3-13：器件13的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物80，CBP和Ir(ppy) 3的质量比为80:20。
实施例3-14：器件14的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物128，CBP和Ir(ppy) 3的质量比为80:20。
实施例3-15：器件15的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物137，CBP和Ir(ppy) 3的质量比为80:20。
实施例3-16：器件16的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物150，CBP和Ir(ppy) 3的质量比为80:20。
实施例3-17：器件17的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物162，CBP和Ir(ppy) 3的质量比为80:20。
实施例3-18：器件18的制备
本实施例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为化合物162，CBP和Ir(ppy) 3的质量比为80:20。
对比例：
对比例与实施例3-1的不同之处在于：OLED器件的发光层主体材料为CBP，空穴阻挡/电子传输层材料为TPBI。
制备好上述电致发光器件后，测量器件的驱动电压，电流效率，其结果如表3所示。
表3
编号 电流效率(cd/A) 色彩 LT95寿命(Hr)@5000nits
器件1 48.7 绿光 37.1
器件2 49.2 绿光 46.3
器件3 48.8 绿光 44.9
器件4 49.0 绿光 45.5
器件5 55.2 绿光 45.3
器件6 56.7 绿光 37.4
器件7 51.9 绿光 46.9
器件8 52.7 绿光 45.4
器件9 45.3 绿光 27.1
器件10 45.2 绿光 34.9
器件11 44.9 绿光 27.0
器件12 44.5 绿光 35.7
器件13 45.0 绿光 35.1
器件14 44.2 绿光 34.8
器件15 44.8 绿光 35.6
器件16 45.1 绿光 35.8
器件17 44.3 绿光 34.9
对比例 28 绿光 2.5
注：寿命测试系统为本发明所有权人与上海大学共同研究的OLED器件寿命测试仪。
由表3的结果可以看出，本发明制备的以氮杂螺芴和芳基酮为核心的化合物可应用于OLED发光器件制作，并且与对比例相比，无论是效率还是寿命均比已知OLED材料获得较大改观，特别是器件的寿命衰减获得较大的提升。
本发明的化合物制备的OLED器件在低温下工作时效率也比较稳定，将器件1、5、11和器件对比例在-10～80℃区间进行效率测试，所得结果如表4和图2所示：
表4
Figure PCTCN2018110694-appb-000040
从表4和图2的数据可知，器件1、6、12为本发明材料和已知材料搭配的器件结构，和器件对比例相比，不仅低温效率高，而且在温度升高过程中，效率平稳升高。
以上所述仅为本发明的较佳实施例，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、改进等，均应包含在本发明的保护范围之内。

Claims (12)

  1. 一种以氮杂螺芴和芳基酮为核心的化合物，其特征在于，该化合物的结构如通式(1)所示：
    Figure PCTCN2018110694-appb-100001
    其中，X独立的表示为N或CH，且至少一个X为N；
    Z表示为O、S、C 1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基中的一种，i等于0或1；
    L表示为单键、经取代或未经取代的C 6至C 30亚芳基、经取代或未经取代的C 5至C 30亚杂芳基中的一种。
  2. 根据权利要求1所述的化合物，其特征在于，通式(1)中，X表示为N的数量为1、2或4。
  3. 根据权利要求2所述的化合物，其特征在于，当X表示为N的数量为2或4时，N在氮杂螺芴基团中所处的位置对称。
  4. 根据权利要求1所述的化合物，其特征在于，L表示为亚苯基、亚联苯基或亚萘基中的一种。
  5. 根据权利要求1-4任一项所述的化合物，其特征在于，所述化合物的具体结构式为以下任意一种：
    Figure PCTCN2018110694-appb-100002
    Figure PCTCN2018110694-appb-100003
    Figure PCTCN2018110694-appb-100004
    Figure PCTCN2018110694-appb-100005
    Figure PCTCN2018110694-appb-100006
    Figure PCTCN2018110694-appb-100007
    Figure PCTCN2018110694-appb-100008
    Figure PCTCN2018110694-appb-100009
    Figure PCTCN2018110694-appb-100010
    Figure PCTCN2018110694-appb-100011
  6. 一种如权利要求1-5任一项所述的化合物的制备方法，其特征在于，包括如下步骤：
    在惰性气体保护下，将原料A溶解于四氢呋喃中，加入中间体A和Pd(PPh 3) 4，搅拌，再加入K 2CO 3溶液，将上述反应物的混合溶液于80℃下加热回流5-20h，反应结束后，在上述混合溶液中冷却加水，用二氯甲烷萃取，萃取液用无水硫酸钠干燥，过滤，得到的滤液减压浓缩，所得残余物过硅胶柱纯化，得到目标化合物；
    制备过程中发生的反应方程式为：
    Figure PCTCN2018110694-appb-100012
  7. 根据权利要求6所述的化合物的制备方法，其特征在于，原料A与中间体A的摩尔比为原料A：中间体A＝1:1.0-1.5；Pd(PPh 3) 4与原料A的摩尔比为Pd(PPh 3) 4：原料A＝0.001-0.02:1；K 2CO 3与原料A的摩尔比为K 2CO 3：原料A＝1.0-2.0:1；THF与原料A的用量比为1g原料A加入10-30ml THF。
  8. 如权利要求1-5任一项所述的以氮杂螺芴和芳基酮为核心的化合物在制备有机电致发光器件中的应用。
  9. 一种有机电致发光器件，包括至少一层功能层，其特征在于，所述功能层所用材料含有权利要求1-5任一项所述的以氮杂螺芴和芳基酮为核心的化合物。
  10. 一种有机电致发光器件，包括空穴阻挡层/电子传输层，其特征在于，所述空穴阻挡层/电子传输层所用材料含有权利要求1-5任一项所述的以氮杂螺芴和芳基酮为核心的化合物。
  11. 一种有机电致发光器件，包括发光层，其特征在于，所述发光层所用材料含有权利要求1-5任一项所述的以氮杂螺芴和芳基酮为核心的化合物。
  12. 一种照明或显示元件，其特征在于，包括如权利要求9-11任一项所述的有机电致发光器件。
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