WO2020248755A1 - 含氮化合物、有机电致发光器件和光电转化器件 - Google Patents

含氮化合物、有机电致发光器件和光电转化器件 Download PDF

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WO2020248755A1
WO2020248755A1 PCT/CN2020/089879 CN2020089879W WO2020248755A1 WO 2020248755 A1 WO2020248755 A1 WO 2020248755A1 CN 2020089879 W CN2020089879 W CN 2020089879W WO 2020248755 A1 WO2020248755 A1 WO 2020248755A1
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substituted
carbon atoms
unsubstituted
nitrogen
containing compound
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PCT/CN2020/089879
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French (fr)
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马天天
聂齐齐
李红燕
冯震
孙占义
王亚龙
沙荀姗
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陕西莱特光电材料股份有限公司
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Priority claimed from CN201910515733.1A external-priority patent/CN110128279A/zh
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Priority to KR1020217037104A priority Critical patent/KR20220022053A/ko
Publication of WO2020248755A1 publication Critical patent/WO2020248755A1/zh

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Definitions

  • the present disclosure relates to the technical field of electronic components, in particular to a nitrogen-containing compound, an organic electroluminescence device using the nitrogen-containing compound, and a photoelectric conversion device using the nitrogen-containing compound.
  • This type of electronic components usually includes a cathode and an anode arranged oppositely, and a functional layer arranged between the cathode and the anode.
  • the functional layer is composed of multiple organic or inorganic film layers, and generally includes an energy conversion layer, a hole transport layer between the energy conversion layer and the anode, and an electron transport layer between the energy conversion layer and the cathode.
  • an organic electroluminescence device as an example, it generally includes an anode, a hole transport layer, an electroluminescence layer as an energy conversion layer, an electron transport layer, and a cathode that are stacked in sequence.
  • the two electrodes When voltage is applied to the cathode and anode, the two electrodes generate an electric field. Under the action of the electric field, the electrons on the cathode side move to the electroluminescent layer, and the holes on the anode side also move to the light emitting layer. The electrons and holes are combined in the electroluminescent layer. Excitons are formed, and the excitons are in an excited state and release energy outwards, thereby making the electroluminescent layer emit light to the outside.
  • KR1020190035567A, CN107459466A, CN106008424A, CN104583176A, CN103108859A, etc. disclose materials that can prepare hole transport layers in organic electroluminescent devices. However, it is still necessary to continue to develop new materials to further improve the performance of electronic components.
  • the purpose of the present disclosure is to provide a nitrogen-containing compound, an organic electroluminescent device using the nitrogen-containing compound, and a photoelectric conversion device using the nitrogen-containing compound, for improving the performance of the organic electroluminescent device and the photoelectric conversion device.
  • a nitrogen-containing compound is provided, and the structure of the nitrogen-containing compound is shown in Chemical Formula 1:
  • L is selected from: single bond, substituted or unsubstituted arylene group with 6-30 carbon atoms, substituted or unsubstituted heteroarylene group with 1-30 carbon atoms;
  • Ar 1 and Ar 2 are each independently selected from: substituted or unsubstituted alkyl groups having 1 to 35 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 35 carbon atoms, substituted or unsubstituted carbon atoms 2-35 alkynyl, substituted or unsubstituted cycloalkyl with 3-35 carbon atoms, substituted or unsubstituted heterocycloalkyl with 2-35 carbon atoms, substituted or unsubstituted carbon Aralkyl with 7-30 atoms, substituted or unsubstituted heteroaralkyl with 2-30 carbon atoms, substituted or unsubstituted aryl with 6-30 carbon atoms, substituted or unsubstituted Heteroaryl groups with 1-30 carbon atoms;
  • the substituents of Ar 1 , Ar 2 and L are each independently selected from: deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl with 1-40 carbon atoms, substituted or unsubstituted Cycloalkyl groups with 3-40 carbon atoms, substituted or unsubstituted alkenyl groups with 2-40 carbon atoms, substituted or unsubstituted alkynyl groups with 2-40 carbon atoms, substituted or unsubstituted carbon atoms 2 -40 heterocycloalkyl, substituted or unsubstituted aralkyl with 7-40 carbon atoms, substituted or unsubstituted heteroaralkyl with 2-40 carbon atoms, substituted or unsubstituted 6 carbon atoms -40 aryl groups, substituted or unsubstituted heteroaryl groups with 1-40 carbon atoms, substituted or unsubstituted alkoxy groups with 1-40 carbon atom
  • the Ar 1 is not 9,9-diphenyl fluorene; the Ar 2 is not 9,9-diphenyl fluorene.
  • an organic electroluminescent device comprising an anode and a cathode arranged oppositely, and a functional layer arranged between the anode and the cathode;
  • the functional layer includes the nitrogen-containing compound described above.
  • a photoelectric conversion device comprising an anode and a cathode disposed oppositely, and a functional layer disposed between the anode and the cathode; the functional layer includes The above-mentioned nitrogen-containing compounds.
  • the nitrogen-containing compound has good hole transport characteristics and can be applied to an organic electroluminescence device And between the anode and the energy conversion layer of the photoelectric conversion device to improve the hole transport efficiency between the anode and the energy conversion layer, thereby increasing the luminous efficiency of the organic electroluminescence device and the power generation efficiency of the photoelectric conversion device.
  • the nitrogen-containing compound also has higher electron tolerance and film-forming properties, and can improve the efficiency and lifetime of organic electroluminescent devices and photoelectric conversion devices.
  • the nitrogen-containing compound also has better thermal stability and can maintain a stable structure at high temperatures for a long time, which not only ensures the uniformity and stability of the organic electroluminescent devices and photoelectric conversion devices prepared in different stages, but also ensures The performance of organic electroluminescent devices and photoelectric conversion devices prepared in the later stage of mass production does not decrease.
  • FIG. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present disclosure.
  • FIG. 2 is a schematic diagram of the structure of a photoelectric conversion device according to an embodiment of the present disclosure.
  • Anode; 200 cathode; 300, functional layer; 310, hole injection layer; 320, hole transport layer; 321, first hole transport layer; 322, second hole transport layer; 330, organic electro Light-emitting layer; 340, hole blocking layer; 350, electron transport layer; 360, electron injection layer; 370, photoelectric conversion layer.
  • the present disclosure provides a nitrogen-containing compound whose structure is shown in Chemical Formula 1:
  • L is selected from: single bond, substituted or unsubstituted arylene group with 6-30 carbon atoms, substituted or unsubstituted heteroarylene group with 1-30 carbon atoms;
  • Ar 1 and Ar 2 are each independently selected from: substituted or unsubstituted alkyl groups having 1 to 35 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 35 carbon atoms, substituted or unsubstituted carbon atoms 2-35 alkynyl, substituted or unsubstituted cycloalkyl with 3-35 carbon atoms, substituted or unsubstituted heterocycloalkyl with 2-35 carbon atoms, substituted or unsubstituted carbon Aralkyl with 7-30 atoms, substituted or unsubstituted heteroaralkyl with 2-30 carbon atoms, substituted or unsubstituted aryl with 6-30 carbon atoms, substituted or unsubstituted Heteroaryl groups with 1-30 carbon atoms;
  • the substituents of Ar 1 , Ar 2 and L are each independently selected from: deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl with 1-40 carbon atoms, substituted or unsubstituted Cycloalkyl groups with 3-40 carbon atoms, substituted or unsubstituted alkenyl groups with 2-40 carbon atoms, substituted or unsubstituted alkynyl groups with 2-40 carbon atoms, substituted or unsubstituted carbon atoms 2 -40 heterocycloalkyl, substituted or unsubstituted aralkyl with 7-40 carbon atoms, substituted or unsubstituted heteroaralkyl with 2-40 carbon atoms, substituted or unsubstituted 6 carbon atoms -40 aryl groups, substituted or unsubstituted heteroaryl groups with 1-40 carbon atoms, substituted or unsubstituted alkoxy groups with 1-40 carbon atom
  • the Ar 1 is not 9,9-diphenyl fluorene; the Ar 2 is not 9,9-diphenyl fluorene.
  • the number of carbon atoms of L, Ar 1 and Ar 2 refers to all the carbon atoms.
  • L is selected from a substituted arylene group having 12 carbon atoms, all carbon atoms of the arylene group and the substituents thereon are 12.
  • an unsubstituted alkyl group having 1 to 35 carbon atoms refers to a straight chain alkyl group having 1 to 35 carbon atoms, or a branched alkyl group having 1 to 13 carbon atoms.
  • the substituted alkyl group having 1 to 35 carbon atoms means that at least one hydrogen atom is substituted with a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, or the like.
  • the alkyl group is an alkyl group having 1 to 4 carbon atoms. For example: methyl, ethyl, propyl, isopropyl, tert-butyl.
  • an unsubstituted alkenyl group with 2 to 35 carbon atoms refers to an alkenyl group with 2 to 35 carbon atoms, and a straight chain alkene with 2 to 35 carbon atoms containing a carbon-carbon double bond Group, or a branched alkenyl group containing 1-13 carbon atoms.
  • the substituted alkenyl group having 2 to 35 carbon atoms means that at least one hydrogen atom is replaced by a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, or the like.
  • an unsubstituted alkynyl group with 2 to 35 carbon atoms refers to an alkynyl group with 2 to 35 carbon atoms, and a straight chain alkyne with 2 to 35 carbon atoms containing a carbon-carbon triple bond Group, or a branched alkynyl group containing 1-10 carbon atoms.
  • the substituted alkynyl group having 2 to 35 carbon atoms means that at least one hydrogen atom is replaced by a deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, and the like.
  • the nitride-containing compound of the present disclosure has good hole transport efficiency, and therefore can be used as a material for transporting holes in organic electroluminescence devices and photoelectric conversion devices.
  • the nitrogen-containing compound of the present disclosure may be applied between the anode of an organic electroluminescent device and the organic electroluminescent layer, so as to transport holes on the anode to the organic electroluminescent layer.
  • the nitrogen-containing compound of the present disclosure can be applied to any one or more of the hole injection layer, the hole transport layer, and the electron blocking layer of an organic electroluminescent device.
  • the nitrogen-containing compound of the present disclosure may be applied between the anode of the photoelectric conversion device and the photoelectric conversion layer, so as to transport holes on the photoelectric conversion layer to the anode.
  • the substituents of Ar 1 , Ar 2 and L are each independently selected from: deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted carbon atoms 1- 33 alkyl, substituted or unsubstituted cycloalkyl with 3 to 33 carbon atoms, substituted or unsubstituted alkenyl with 2 to 33 carbon atoms, substituted or unsubstituted alkynyl with 2 to 33 carbon atoms , Substituted or unsubstituted heterocycloalkyl groups with 2-33 carbon atoms, substituted or unsubstituted aralkyl groups with 7-33 carbon atoms, substituted or unsubstituted heteroaralkyl groups with 2-33 carbon atoms , Substituted or unsubstituted aryl groups having 6 to 33 carbon atoms, substituted or unsubstituted heteroaryl groups having 1 to 33 carbon atom
  • L is selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted phenylene Terphenyl, substituted or unsubstituted fluorenylene.
  • the relative molecular mass of the nitrogen-containing compound is not greater than 750, so as to ensure that the nitrogen-containing compound of the present disclosure has good thermal stability, and to ensure that the nitrogen-containing compound of the present disclosure is vaporized for a long time. Keep the structure stable during the process.
  • L is selected from a single bond, a substituted or unsubstituted arylene group having 6-12 carbon atoms.
  • L is selected from a single bond or an unsubstituted arylene group having 6-12 carbon atoms.
  • L is selected from a single bond or the following substituents:
  • Ar 1 and Ar 2 are independently selected from substituted or unsubstituted aryl groups with 6-20 carbon atoms, substituted or unsubstituted heterocyclic groups with 12-20 carbon atoms. Aryl.
  • Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted aryl groups having 6-25 carbon atoms, and the Ar 1 is not 9,9-diphenyl Fluorene, the Ar 2 is not 9,9-diphenyl fluorene.
  • At least one of Ar 1 and Ar 2 is selected from substituted aryl groups having 6-12 ring carbon atoms, and the substituted ring-forming carbon atoms are 6-12
  • the substituents on the aryl group are selected from: aryl groups having 6 to 14 carbon atoms and heteroaryl groups having 6 to 12 carbon atoms.
  • Ar 1 is Then, Ar 1 is a substituted aryl group having 6 ring carbon atoms, and the substituent on the substituted aryl group having 6 ring carbon atoms is a heteroaryl group having 12 carbon atoms.
  • Ar 1 and Ar 2 are each independently selected from the following substituents:
  • Ar 1 and Ar 2 are each independently selected from the following substituents:
  • Ar 1 and Ar 2 are each independently selected from the following substituents:
  • the nitrogen-containing compound is selected from the following compounds:
  • the nitrogen-containing compound of the present disclosure introduces an adamantane-2-yl structure at the 9 position of fluorene.
  • the adamantyl group can increase the electron density of the fluorene ring and the entire conjugated system of the nitrogen-containing compound through the hyperconjugation effect, and increase the The hole conduction efficiency of the nitrogen compound further improves the carrier conduction efficiency and lifetime of the organic electroluminescence device and the photoelectric conversion device.
  • the adamantane-2-yl group is introduced into the 9 position of fluorene instead of the terminal, and then introduced between the side chains of the amine of the nitrogen-containing compound of the present disclosure instead of the terminal.
  • the large steric hindrance of adamantane-2-yl can adjust the angle and the degree of conjugation between the branches of the amine, and then adjust the HOMO value of the nitrogen-containing compound, so that the HOMO value of the nitrogen-containing compound can be compared with
  • the adjacent film layers are more matched, which can reduce the driving voltage of the organic electroluminescence device or increase the open circuit voltage of the photoelectric conversion device.
  • the nitrogen-containing compound of the present disclosure uses a bulky alkyl structure to modify the fluorene group. Compared with the modification using an aryl group, the excessive ⁇ - ⁇ stacking effect can be avoided, and the fluorene group can be reduced.
  • the symmetry of the nitrogen-containing compound can further improve the film-forming properties of the nitrogen-containing compound.
  • adamantane-2-yl can ensure that the nitrogen-containing compound of the present disclosure has a suitable molecular weight, thereby ensuring that the nitrogen-containing compound of the present disclosure has a suitable glass transition temperature, and improve the preparation of organic electroluminescent devices and photoelectric conversion devices. The physical and thermal stability.
  • the present disclosure also provides an organic electroluminescence device.
  • the organic electroluminescent device includes an anode 100 and a cathode 200 disposed oppositely, and a functional layer 300 disposed between the anode 100 and the cathode 200; the functional layer 300 includes the nitrogen-containing compound provided in the present disclosure. .
  • the nitrogen-containing compound provided in the present disclosure can be used to form at least one organic film layer in the functional layer 300 to improve the performance of the organic electroluminescent device, especially to improve the organic electroluminescent device.
  • the lifetime of the organic electroluminescent device is improved, the driving voltage of the organic electroluminescent device is reduced, or the performance of the mass-produced organic electroluminescent device is uniform and stable.
  • the functional layer 300 includes a hole transport layer 320, and the hole transport layer 320 includes the nitrogen-containing compound provided in the present disclosure.
  • the hole transport layer 320 may be composed of the nitrogen-containing compound provided in the present disclosure, or may be composed of the nitrogen-containing compound provided in the present disclosure and other materials.
  • the hole transport layer 320 includes a first hole transport layer 321 and a second hole transport layer 322, and the first hole transport layer 321 is disposed on the surface of the second hole transport layer 322 close to the anode 100;
  • a hole transport layer 321 or a second hole transport layer 322 includes the nitrogen-containing compound provided in the present disclosure.
  • the first hole transport layer 321 or the second hole transport layer 322 may contain the nitrogen-containing compound provided in the present disclosure, or the first hole transport layer 321 and the second hole transport layer 322 All contain the nitrogen-containing compound provided by the present disclosure. It can be understood that the first hole transport layer 321 or the second hole transport layer 322 may also contain other materials, or may not contain other materials.
  • the first hole transport layer 321 or the second hole transport layer 322 is composed of the nitrogen-containing compound provided in the present disclosure.
  • the functional layer 300 includes a hole injection layer 310, and the hole injection layer 310 may include the nitrogen-containing compound provided in the present disclosure.
  • the hole injection layer 310 may be composed of the nitrogen-containing compound provided in the present disclosure, or may be composed of the nitrogen-containing compound provided in the present disclosure and other materials.
  • the hole injection layer 310 is composed of the nitrogen-containing compound provided in the present disclosure.
  • the anode 100 includes the following anode material, which is preferably a material with a large work function (work function) that facilitates injection of holes into the functional layer.
  • anode materials include: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combined metals and oxides such as ZnO: Al or SnO 2 : Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene ] (PEDT), polypyrrole and polyaniline, but not limited thereto. It is preferable to include a transparent electrode containing indium tin oxide (ITO) as an anode.
  • ITO indium tin oxide
  • the cathode 200 includes the following cathode material, which is a material with a small work function that facilitates injection of electrons into the functional layer.
  • cathode materials include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or their alloys; or multilayer materials such as LiF/Al, Liq/ Al, LiO 2 /Al, LiF/Ca, LiF/Al, and BaF 2 /Ca, but not limited thereto. It is preferable to include a metal electrode containing aluminum as a cathode.
  • an organic electroluminescent device may include an anode 100, a hole injection layer 310, a hole transport layer 320, an organic electroluminescence layer 330, and a cavity which are sequentially stacked.
  • at least one of the hole injection layer 310 and the hole transport layer 320 contains the nitrogen-containing compound of the present disclosure.
  • the present disclosure also provides a photoelectric conversion device.
  • the photoelectric conversion device may include an anode 100 and a cathode 200 disposed oppositely, and a functional layer 300 disposed between the anode 100 and the cathode 200; the functional layer 300 includes The nitrogen-containing compound provided by the present disclosure.
  • the nitrogen-containing compound provided in the present disclosure can be used to form at least one organic thin layer in the functional layer 300 to improve the performance of the photoelectric conversion device, especially to increase the life of the photoelectric conversion device and increase The open circuit voltage of the photoelectric conversion device or the performance of the mass-produced photoelectric conversion device is uniform and stable.
  • the functional layer 300 includes a hole transport layer 320, and the hole transport layer 320 includes the nitrogen-containing compound of the present disclosure.
  • the hole transport layer 320 may be composed of the nitrogen-containing compound provided in the present disclosure, or may be composed of the nitrogen-containing compound provided in the present disclosure and other materials.
  • the hole transport layer 320 may further include inorganic dopant materials to improve the hole transport performance of the hole transport layer 320.
  • the photoelectric conversion device may include an anode 100, a hole transport layer 320, a photoelectric conversion layer 370, an electron transport layer 350, and a cathode 200 that are sequentially stacked and arranged.
  • the photoelectric conversion device may be a solar cell, especially an organic thin film solar cell.
  • the magnesium bar (13.54 g, 564 mmol) and ether (100 mL) were placed in a round-bottomed flask dried under nitrogen protection, and iodine (100 mg) was added. Then, a solution of 2'-bromo-4-chlorobiphenyl (50.00g, 187.0mmol) in ethyl ether (200mL) was slowly dropped into the flask. After the addition, the temperature was raised to 35°C and stirred for 3 hours; the reaction solution was reduced At 0°C, slowly drop a solution of adamantanone (22.45g, 149mmol) in ether (200mL) into it.
  • Table 1 Compound structure, preparation and characterization data
  • the compound When the compound is used for mass production of devices, it needs to be heated for a long time under evaporation conditions. If the thermal stability of the molecular structure of the compound is poor under heated conditions, the purity of the compound will decrease under long-term heating conditions, resulting in large differences in the performance of devices prepared before, during, and after mass production.
  • the present disclosure uses the following methods to evaluate the stability of the molecular structure of the nitrogen-containing compound of the present disclosure under long-term heating during mass production evaporation:
  • the purity reduction value of the nitrogen-containing compounds of the present disclosure are all less than 0.7%, and most of them are less than 0.3%.
  • the decrease in purity exceeded 1%. Therefore, the thermal stability of the nitrogen-containing compound of the present disclosure is much better than that of Comparative Example 1 and Comparative Example 2.
  • the purity of the compound material decreases by more than 1%, the efficiency and life of the device will be significantly reduced; therefore, the use of such thermally unstable compounds in actual mass production will cause the performance of the devices prepared in the middle and late stages of mass production. Big difference.
  • the molecular weights of compounds 1-30 are relatively small, and thus have a relatively low vapor deposition temperature.
  • the heat resistance experiment has confirmed that the purity decline value is less than 0.7%. Therefore, the nitrogen-containing compounds of the present disclosure have excellent mass heat production stability.
  • the blue organic electroluminescent device is prepared by the following method
  • the ITO thickness is The ITO substrate (manufactured by Corning) was cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (thickness).
  • the photolithography process was used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns.
  • Ozone and O 2 :N 2 plasma are used for surface treatment to increase the work function of the anode (experimental substrate) and remove scum.
  • M-MTDATA was vacuum evaporated on the experimental substrate (anode) to form a thickness of The hole injection layer (HIL), and the compound 1 is vacuum evaporated on the hole injection layer to form a thickness of The first hole transport layer.
  • HIL hole injection layer
  • TCTA was evaporated on the first hole transport layer to form a thickness of The second hole transport layer.
  • the thickness is The light-emitting layer (EML).
  • DBimiBphen and LiQ are mixed at a weight ratio of 1:1 and formed by evaporation Thick electron transport layer (ETL), LiQ is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at a deposition rate of 1:9, and then vacuum-evaporated on the electron injection layer to form a thickness of The cathode.
  • ETL Thick electron transport layer
  • Mg magnesium
  • Ag silver
  • the vapor deposition thickness on the above cathode is CP-1, thus completing the manufacture of organic light-emitting devices.
  • each material used is as follows:
  • Example 2 Using the first hole transport layer material listed in Table 4 instead of Compound 1 in Example 1, the corresponding blue organic electroluminescent device was prepared in the same manner as in Example 1.
  • Example 2 Compound 2 was used instead of Compound 1 to prepare a blue organic electroluminescent device; in Example 3, Compound 4 was used instead of Compound 1 to prepare a blue organic electroluminescent device; in Example 4, A blue organic electroluminescent device was prepared by using compound 6 instead of compound 1; in Example 5, a blue organic electroluminescent device was prepared by using compound 7 instead of compound 1; in Example 6, a blue organic electroluminescent device was prepared by using compound 9 instead of compound 1 Color organic electroluminescence device; in Example 7, compound 10 was used instead of compound 1 to prepare a blue organic electroluminescence device.
  • Example 4 Use the first hole transport layer material listed in Table 4 to replace compound 1 in Example 1, and use the second hole transport layer material listed in Table 2 to replace the TCTA in Example 1. In the same way as in Example 1, the corresponding blue organic electroluminescent device was prepared.
  • Example 8 a blue organic electroluminescent device was prepared by using NPB instead of compound 1 and using compound 8 instead of TCTA; in Example 9, a blue organic electroluminescent device was prepared by using NPB instead of compound 1 and using compound 24 instead of TCTA.
  • Light-emitting device In Example 10, NPB was used instead of Compound 1 and Compound 25 was used instead of TCTA to prepare a blue organic electroluminescent device; In Example 11, NPB was used instead of Compound 1 and Compound 27 was used instead of TCTA to prepare blue organic light emitting devices.
  • Example 12 NPB was used instead of Compound 1 and Compound 28 was used instead of TCTA to prepare blue organic electroluminescent devices; In Example 13, NPB was used instead of Compound 1 and Compound 29 was used instead of TCTA to prepare blue Color organic electroluminescent device.
  • NPB NPB
  • the blue organic electroluminescent devices prepared in Examples 1 to 7 have lower driving voltage and more High external quantum efficiency and longer lifetime.
  • the driving voltage of the blue organic electroluminescent devices prepared in Examples 1-7 is reduced by 9.5% at the maximum, the external quantum efficiency is increased by at least 16.8%, and the T95 lifetime is at least extended Up 69.5%. Specifically, this is a very significant improvement for blue light devices.
  • the blue organic electroluminescent devices prepared in Examples 8 to 13 have lower driving voltage and more High current efficiency and external quantum efficiency, longer life.
  • the driving voltage of the blue organic electroluminescent devices prepared in Examples 8-13 is reduced by 6.4% at the maximum, the current efficiency is increased by at least 21.1%, and the external quantum efficiency is at least increased.
  • the life of T95 is extended by at least 69%. This is a very significant improvement for blue light devices.
  • EQE% light extraction rate * internal quantum efficiency (light extraction rate is less than 1).
  • the organic light-emitting layer uses fluorescent materials, and the fluorescent materials emit singlet excitons, and their internal quantum efficiency limit value is 25%.
  • the theoretical limit value of the external quantum efficiency of the blue organic electroluminescent device is 25%.
  • the external quantum efficiency of the blue organic electroluminescent device prepared in Examples 1-7 is at least increased from 10.7% to 12.9%. Compared with the theoretical limit value, the increase rate reaches 17.6%, which is a very significant increase.
  • the theoretical limit value is 25%, compared with Comparative Example 1 and Comparative Example 3, the external quantum efficiency of the blue organic electroluminescent devices prepared in Examples 8-13 is at least increased from 10.4% to 13.5%. Compared with the theoretical limit value, the increase rate reaches 15.9%, which is a very significant increase.
  • the nitrogen-containing compound of the present disclosure when used to prepare an organic electroluminescent device, it can effectively reduce the driving voltage of the electroluminescent device, improve the external quantum efficiency and extend the life of the organic electroluminescent device.
  • the red organic electroluminescent device is prepared by the following method:
  • the ITO thickness is The ITO substrate (manufactured by Corning) was cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (height).
  • the photolithography process was used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns.
  • Ozone and O 2 :N 2 plasma are used for surface treatment to increase the work function of the anode (experimental substrate) and remove scum.
  • M-MTDATA was vacuum evaporated on the experimental substrate (anode) to form a thickness of The hole injection layer (HIL), and the compound 11 is evaporated on the hole injection layer to form a thickness of The first hole transport layer.
  • HIL hole injection layer
  • the compound TPD was vacuum evaporated on the first hole transport layer to form a thickness of The second hole transport layer.
  • CBP was vapor-deposited on the second hole transport layer as the main body, and Ir(piq) 2 (acac) was simultaneously doped according to the film thickness ratio of 100:3 to form a thickness of The light-emitting layer (EML).
  • EML The light-emitting layer
  • DBimiBphen and LiQ are mixed at a weight ratio of 1:1 and formed by evaporation Thick electron transport layer (ETL), LiQ is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL), and then magnesium (Mg) and silver (Ag) are mixed at an evaporation rate of 1:9, and then vacuum evaporated on the electron injection layer to form a thickness of The cathode.
  • the vapor deposition thickness on the above cathode is CP-1 to form an organic cover layer (CPL).
  • TPD TPD
  • CBP CBP
  • Example 14 Using the first hole transport layer material listed in Table 5 instead of Compound 11 in Example 14, the corresponding red organic electroluminescent device was prepared according to the same method as in Example 14.
  • Example 15 compound 12 was used instead of compound 11 to prepare a red organic electroluminescent device; in Example 16, compound 13 was used instead of compound 11 to prepare a red organic electroluminescent device; in Example 17, compound 14 instead of compound 11 to prepare a red organic electroluminescence device; in Example 18, compound 18 was used instead of compound 11 to prepare a red organic electroluminescence device; in Example 19, compound 19 was used instead of compound 11 to prepare a red organic electroluminescence device Device; In Example 20, compound 20 was used instead of compound 11 to prepare a red organic electroluminescent device.
  • the first hole transport layer material listed in Table 5 was used to replace compound 11 in Example 14, and the second hole transport layer material listed in Table 5 was used to replace the TPD in Example 14. In the same way as in Example 14, the corresponding red organic electroluminescence device was prepared.
  • Example 21 NPB was used instead of Compound 11 and Compound 3 was used instead of TPD to prepare a red organic electroluminescence device; in Example 22, NPB was used instead of Compound 11 and Compound 5 was used instead of TPD to prepare a red organic electroluminescence device.
  • Example 23 using NPB instead of compound 11 and using compound 15 instead of TPD to prepare a red organic electroluminescence device; in Example 24, using NPB instead of compound 11 and using compound 16 instead of TPD to prepare red organic electroluminescence Device; in Example 25, using NPB instead of compound 11 and using compound 17 instead of TPD to prepare a red organic electroluminescence device; in Example 26, using NPB instead of compound 11 and using compound 21 instead of TPD to prepare red organic electroluminescence Device; In Example 27, NPB was used instead of Compound 11 and Compound 22 was used instead of TPD to prepare a red organic electroluminescence device; in Example 28, NPB was used instead of Compound 11 and Compound 23 was used instead of TPD to prepare red organic electroluminescence. Device; in Example 29, using NPB instead of compound 11 and using compound 26 instead of TPD to prepare red organic electroluminescence devices; in Example 30, using NPB instead of compound 11 and using compound 30 instead of TPD to prepare red organic electroluminescence Device.
  • the IVL performance of the device was tested under the condition of 10 mA/cm 2 , and the lifetime of the T95 device was tested at a constant current density of 20 mA/cm 2.
  • the test results are shown in Table 5.
  • the red organic electroluminescent devices prepared in Examples 14-20 have lower driving voltage and higher external quantum efficiency. And a longer life.
  • the driving voltage of the red organic electroluminescent devices prepared in Examples 14-20 was reduced by at least 4.4%, the current efficiency was increased by at least 20.8%, and the external quantum efficiency was increased by at least 20.5%.
  • the life span is extended by at least 163%.
  • the red organic electroluminescent devices prepared in Examples 21-30 have lower driving voltage and higher The current efficiency and external quantum efficiency, longer life.
  • the driving voltage of the red organic electroluminescent device prepared in Examples 21-30 was reduced by at least 4.6%, the current efficiency was increased by at least 16.3%, and the external quantum efficiency was increased by at least 15.7%, the life of T95 is extended by at least 154%.
  • the nitrogen-containing compound of the present disclosure when used to prepare an organic electroluminescent device, it can effectively reduce the driving voltage of the electroluminescent device, improve the external quantum efficiency and extend the life of the organic electroluminescent device.
  • the blue organic electroluminescent device is prepared by the following method
  • the ITO thickness is The ITO substrate (manufactured by Corning) was cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (thickness).
  • the photolithography process was used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns.
  • Ozone and O 2 :N 2 plasma are used for surface treatment to increase the work function of the anode (experimental substrate) and remove scum.
  • M-MTDATA was vacuum evaporated on the experimental substrate (anode) to form a thickness of The hole injection layer (HIL), and vacuum evaporation of compound 2 on the hole injection layer to form a thickness of The first hole transport layer.
  • HIL hole injection layer
  • TCTA was evaporated on the first hole transport layer to form a thickness of The second hole transport layer.
  • DBimiBphen and LiQ are mixed at a weight ratio of 1:1 and formed by evaporation Thick electron transport layer (ETL), LiQ is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at a deposition rate of 1:9, and then vacuum deposited on the electron injection layer to form a thickness of The cathode.
  • ETL Thick electron transport layer
  • Mg magnesium
  • Ag silver
  • the vapor deposition thickness on the above cathode is N-(4-(9H-carbazol-9-yl)phenyl)-4'-(9H-carbazol-9-yl)-N-phenyl-[1,1'-biphenyl]-4 -amine.
  • Example 32 compound 31 was used instead of compound 2 to prepare a blue organic electroluminescent device; in Example 33, compound 3 was used instead of compound 2 to prepare a blue organic electroluminescent device; in Example 34, Compound 32 was used instead of Compound 2 to prepare a blue organic electroluminescent device; in Example 35, Compound 33 was used instead of Compound 2 to prepare a blue organic electroluminescent device.
  • Example 31 Using NPB, NPD, and TPD to replace compound 2 in Example 31, respectively, a blue organic electroluminescent device was prepared according to the same method as in Example 31.
  • NPD and TPD are as follows:
  • the blue organic electroluminescent devices prepared in Examples 31 to 35 have lower driving voltage and more High luminous efficiency, higher external quantum efficiency and longer life.
  • the driving voltage of the blue organic electroluminescent device prepared in Examples 31 to 35 is reduced by at least 5%, the luminous efficiency is increased by at least 17%, and the external quantum efficiency is at least increased By 25.2%, the life of T95 is extended by at least 67%.
  • the nitrogen-containing compound of the present disclosure when used to prepare an organic electroluminescent device, it can effectively reduce the driving voltage of the electroluminescent device, improve the luminous efficiency, increase the external quantum efficiency and extend the life of the organic electroluminescent device.
  • the red organic electroluminescent device is prepared by the following method:
  • the ITO thickness is The ITO substrate (manufactured by Corning) was cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (height).
  • the photolithography process was used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns.
  • Ozone and O 2 :N 2 plasma are used for surface treatment to increase the work function of the anode (experimental substrate) and remove scum.
  • M-MTDATA was vacuum evaporated on the experimental substrate (anode) to form a thickness of Hole injection layer (HIL), and NPB is evaporated on the hole injection layer to form a thickness of The first hole transport layer.
  • HIL Hole injection layer
  • Compound 33 was vacuum-evaporated on the first hole transport layer to form a thickness of The second hole transport layer.
  • CBP was vapor-deposited on the second hole transport layer as the main body, and Ir(piq) 2 (acac) was simultaneously doped according to the film thickness ratio of 35:5 to form a thickness of The light-emitting layer (EML).
  • EML The light-emitting layer
  • DBimiBphen and LiQ are mixed at a weight ratio of 1:1 and formed by evaporation Thick electron transport layer (ETL), LiQ is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL), and then magnesium (Mg) and silver (Ag) are mixed at an evaporation rate of 1:9, and then vacuum evaporated on the electron injection layer to form a thickness of The cathode.
  • the vapor deposition thickness on the above cathode is N-(4-(9H-carbazol-9-yl)phenyl)-4'-(9H-carbazol-9-yl)-N-phenyl-[1,1'-biphenyl]-4 -Amine, which forms an organic cover layer (CPL).
  • Example 36 Using the compounds listed in Table 7 instead of compound 33 in Example 36, according to the same method as in Example 36, the corresponding red organic electroluminescent device was prepared.
  • Example 37 compound 34 was used instead of compound 33 to prepare a red organic electroluminescent device; in Example 38, compound 35 was used instead of compound 33 to prepare a red organic electroluminescent device; in Example 39, compound 36 instead of compound 33 to prepare a red organic electroluminescent device.
  • Example 36 Using NPD instead of Compound 33 in Example 36, a red organic electroluminescent device was prepared according to the same method as in Example 36.
  • Example 36 Using TPD instead of compound 33 in Example 36, according to the same method as in Example 36, a red organic electroluminescent device was prepared.
  • Example 36 According to the same method as in Example 36 without forming the second hole transport layer, a red organic electroluminescent device was prepared.
  • the IVL performance of the device was tested under the condition of 10 mA/cm 2 , and the lifetime of the T95 device was tested at a constant current density of 20 mA/cm 2.
  • the test results are shown in Table 7.
  • the red organic electroluminescent devices prepared in Examples 36 to 39 have lower driving voltage and higher Luminous efficiency, higher external quantum efficiency and longer life.
  • the luminous efficiency of the red organic electroluminescent devices prepared in Examples 36 to 39 is increased by at least 20.7%
  • the external quantum efficiency is increased by at least 15.9%
  • the T95 lifetime is at least extended 59%. Therefore, when the nitrogen-containing compound of the present disclosure is used to prepare an organic electroluminescent device, it can effectively reduce the driving voltage of the electroluminescent device, improve the luminous efficiency, increase the external quantum efficiency and extend the life of the organic electroluminescent device.
  • the nitrogen-containing compound of the present disclosure introduces an adamantane-2-yl structure at the 9 position of fluorene.
  • the adamantyl group can increase the electron density of the fluorene ring and the entire conjugate system of the nitrogen-containing compound through the hyperconjugation effect, thereby increasing the nitrogen
  • the hole conduction efficiency of the compound further improves the carrier conduction efficiency and lifetime of the organic electroluminescence device and the photoelectric conversion device.
  • the adamantane-2-yl group is introduced into the 9 position of fluorene instead of the terminal, and then introduced between the side chains of the amine of the nitrogen-containing compound of the present disclosure instead of the terminal.
  • the large steric hindrance of adamantane-2-yl can adjust the angle and the degree of conjugation between the branches of the amine, and then adjust the HOMO value of the nitrogen-containing compound, so that the HOMO value of the nitrogen-containing compound can be compared with
  • the adjacent film layers are more matched, which in turn can reduce the driving voltage of the organic electroluminescent device and increase the open circuit voltage of the photoelectric conversion device.
  • the nitrogen-containing compound of the present disclosure uses a bulky alkyl structure to modify the fluorene group. Compared with the modification with an aryl group, the nitrogen-containing compound can avoid excessive ⁇ - ⁇ stacking effect and can improve the performance of the nitrogen-containing compound. The stability further improves the life span of organic electroluminescent devices and photoelectric conversion devices. Moreover, modification of the 9-position of fluorene by a large hindered adamantane-2-yl group can reduce the symmetry of the nitrogen-containing compound of the present disclosure, thereby reducing the film-forming properties of the nitrogen-containing compound, and facilitating organic electroluminescence devices And the preparation of photoelectric conversion devices.

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Abstract

一种含氮化合物、有机电致发光器件和光电转化器件，属于电子元器件技术领域。该含氮化合物的结构如化学式1所示。该氮化合物能够提高有机电致发光器件和光电转化器件的性能。

Description

含氮化合物、有机电致发光器件和光电转化器件
相关申请的交叉引用
本公开要求在2019年6月14日提交的中国专利申请号201910515733.1、2019年8月15日提交的中国专利申请号201910755507.0和2019年8月19日提交的中国专利申请号201910765403.8的优先权，以上专利通过引用被全部合并至本公开。
技术领域
本公开涉及电子元器件技术领域，尤其涉及一种含氮化合物、应用该含氮化合物的有机电致发光器件和应用该含氮化合物的光电转化器件。
背景技术
随着电子技术的发展和材料科学的进步，用于实现电致发光或者光电转化的电子元器件的应用范围越来越广泛。该类电子元器件通常包括相对设置的阴极和阳极，以及设置于阴极和阳极之间的功能层。该功能层由多层有机或者无机膜层组成，且一般包括能量转化层、位于能量转化层与阳极之间的空穴传输层、位于能量转化层与阴极之间的电子传输层。
以有机电致发光器件为例，其一般包括依次层叠设置的阳极、空穴传输层、作为能量转化层的电致发光层、电子传输层和阴极。当阴阳两极施加电压时，两电极产生电场，在电场的作用下，阴极侧的电子向电致发光层移动，阳极侧的空穴也向发光层移动，电子和空穴在电致发光层结合形成激子，激子处于激发态向外释放能量，进而使得电致发光层对外发光。
现有技术中，KR1020190035567A、CN107459466A、CN106008424A、CN104583176A、CN103108859A等公开了可以在有机电致发光器件中制备空穴传输层的材料。然而，依然有必要继续研发新型的材料，以进一步提高电子元器件的性能。
发明内容
本公开的目的在于提供一种含氮化合物、应用该含氮化合物的有机电致发光器件和应用该含氮化合物的光电转化器件，用于提高有机电致发光器件和光电转化器件的性能。
为实现上述发明目的，本公开采用如下技术方案：
根据本公开的第一个方面，提供一种含氮化合物，所述含氮化合物的结构如化学式1所示：
Figure PCTCN2020089879-appb-000001
其中，L选自：单键、取代或未取代的碳原子数为6-30的亚芳基、取代或未取代的碳原子数为1-30的亚杂芳基；
Ar 1和Ar 2分别独立地选自：取代或未取代的碳原子数为1-35的烷基、取代或未取代的碳原子数为2-35的烯基、取代或未取代的碳原子数为2-35的炔基、取代或未取代的碳原子数为3-35的环烷基、取代或未取代的碳原子数为2-35的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基；
所述Ar 1、Ar 2以及L的取代基分别独立地选自：氘、氰基、硝基、卤素、羟基、取代或未取代的碳原子数1-40的烷基、取代或未取代的碳原子数3-40的环烷基、取代或未取代的碳原子数2-40的烯基、取代或未取代的碳原子数2-40的炔基、取代或未取代的碳原子数2-40的杂环烷基、取代或未取代的碳原子数7-40的芳烷基、取代或未取代的碳原子数2-40的杂芳烷基、取代或未取代的碳原子数6-40的芳基、取代或未取代的碳原子数1-40的杂芳基、取代或未取代的碳原子数1-40的烷氧基、取代或未取代的碳原子数1-40的烷氨基、取代或未取代的碳原子数6-40的芳氨基、取代或未取代的碳原子数为1-40的烷硫基、取代或未取代的碳原子数7-40的芳烷氨基、取代或未取代的碳原子数1-24的杂芳氨基、取代或未取代的碳原子数为1-45的烷基甲硅烷基、取代或未取代的碳原子数为6-50的芳基甲硅烷基、取代或未取代的碳原子数为6-30的芳氧基、取代或未取代的碳原子数为6-30芳硫基。
在本公开中，所述Ar 1不为9,9-二苯基芴；所述Ar 2不为9,9-二苯基芴。
根据本公开的第二个方面，提供一种有机电致发光器件，所述有机电致发光器件包括相对设置的阳极和阴极，以及设于所述阳极和所述阴极之间的功能层；所述功能层包含上述的含氮化合物。
根据本公开的第三个方面，提供一种光电转化器件，所述光电转化器件包括相对设置的阳极和阴极，以及设于所述阳极和所述阴极之间的功能层；所述功能层包含上述的含氮化合物。
本公开提供的含氮化合物、应用该含氮化合物的有机电致发光器件和应用该含氮化合物的光电转化器件中，含氮化合物具有良好的空穴传输特性，能够应用于有机电致发光器件和光电转化器件的阳极与能量转化层之间，以提高阳极与能量转化层之间的空穴传输效率，进而提高有机电致发光器件的发光效率和光电转化器件的发电效率。该含氮化合物还具有更高的电子耐受度以及成膜性，能够提高有机电致发光器件和光电转化器件的效率和寿命。不仅如此，该含氮化合物还具有更佳的热稳定性，能够在长时间高温下保持结构稳定，既保证了不同阶段制备的有机电致发光器件和光电转化器件的性能均一稳定，又保证了在量产后期制备的有机电致发光器件和光电转化器件的性能不下降。
附图说明
通过参照附图详细描述其示例实施方式，本公开的上述和其它特征及优点将变得更加明显。
图1是本公开实施方式的有机电致发光器件的结构示意图。
图2是本公开实施方式的光电转化器件的结构示意图。
图中主要元件附图标记说明如下：
100、阳极；200、阴极；300、功能层；310、空穴注入层；320、空穴传输层；321、第一空穴传输层；322、第二空穴传输层；330、有机电致发光层；340、空穴阻挡层；350、电子传输层；360、电子注入层；370、光电转化层。
具体实施方式
现在将参考附图更全面地描述示例实施例。然而，示例实施例能够以多种形式实施，且不应被理解为限于在此阐述的范例；相反，提供这些实施例使得本公开将更加全面和完整，并将示例实施例的构思全面地传达给本领域的技术人员。所描述的特征、结构或特性可以以任何合适的方式结合在一个或更多实施例中。在下面的描述中，提供许多具体细节从而给出对本公开的实施例的充分理解。
在图中，为了清晰，可能夸大了区域和层的厚度。在图中相同的附图标记表示相同或类似的结构，因而将省略它们的详细描述。
所描述的特征、结构或特性可以以任何合适的方式结合在一个或更多实施例中。在下面的描述中，提供许多具体细节从而给出对本公开的实施例的充分理解。然而，本领域技术人员将意识到，可以实践本公开的技术方案而没有所述特定细节中的一个或更多，或者可以采用其它的方法、组元、材料等。在其它情况下，不详细示出或描述公知结构、材料或者操作以避免模糊本公开的主要技术创意。
本公开提供了一种含氮化合物，所述含氮化合物的结构如化学式1所示：
Figure PCTCN2020089879-appb-000002
其中，L选自：单键、取代或未取代的碳原子数为6-30的亚芳基、取代或未取代的碳原子数为1-30的亚杂芳基；
Ar 1和Ar 2分别独立地选自：取代或未取代的碳原子数为1-35的烷基、取代或未取代的碳原子数为2-35的烯基、取代或未取代的碳原子数为2-35的炔基、取代或未取代的碳原子数为3-35的环烷基、取代或未取代的碳原子数为2-35的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基；
所述Ar 1、Ar 2以及L的取代基分别独立地选自：氘、氰基、硝基、卤素、羟基、取代或未取代的碳原子数1-40的烷基、取代或未取代的碳原子数3-40的环烷基、取代或未取代的碳原子数2-40的烯基、取代或未取代的碳原子数2-40的炔基、取代或未取代的碳原子数2-40的杂环烷基、取代或未取代的碳原子数7-40的芳烷基、取代或未取代的碳原子数2-40的杂芳烷基、取代或未取代的碳原子数6-40的芳基、取代或未取代的碳原子数1-40的杂芳基、取代或未取代的碳原子数1-40的烷氧基、取代或未取代的碳原子数1-40的烷氨基、取代或未取代的碳原子数6-40的芳氨基、取代或未取代的碳原子数为 1-40的烷硫基、取代或未取代的碳原子数7-40的芳烷氨基、取代或未取代的碳原子数1-24的杂芳氨基、取代或未取代的碳原子数为1-45的烷基甲硅烷基、取代或未取代的碳原子数为6-50的芳基甲硅烷基、取代或未取代的碳原子数为6-30的芳氧基、取代或未取代的碳原子数为6-30芳硫基。
在本公开中，所述Ar 1不为9,9-二苯基芴；所述Ar 2不为9,9-二苯基芴。
在本公开中，L、Ar 1和Ar 2的碳原子数，指的是所有碳原子数。举例而言，若L选自取代的碳原子数为12的亚芳基，则亚芳基及其上的取代基的所有碳原子数为12。
可选的，未取代的碳原子数为1-35的烷基，指的是碳原子数为1-35的直链的烷基，或包含碳原子数为1-13的支链的烷基。例如，甲基、乙基、丙基、异丁基、仲丁基、戊基、异戊基、已基、叔丁基等。取代的碳原子数为1-35的烷基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基等取代。在一些实施方式中，烷基为碳原子数为1-4的烷基。例如：甲基、乙基、丙基、异丙基、叔丁基。
可选的，未取代的碳原子数为2-35的烯基，指的是的碳原子数为2-35的烯基，包含碳碳双键的碳原子数为2-35的直链烯基，或包含碳原子数为1-13的支链的烯基。例如：乙烯基、丙烯基、烯丙基、异丙烯基、2-丁烯基等。取代的碳原子数为2-35的烯基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基等取代。
可选的，未取代的碳原子数为2-35的炔基，指的是的碳原子数为2-35的炔基，包含碳碳三键的碳原子数为2-35的直链炔基，或包含碳原子数为1-10的支链的炔基。例如：乙炔基、2-丙炔基等。取代的碳原子数为2-35的炔基是指至少一个氢原子被氘原子、F、Cl、I、CN、羟基、硝基、氨基等取代。
本公开的含氮化合具有良好的空穴传输效率，因此可以作为传输空穴的材料而应用于有机电致发光器件和光电转化器件中。举例而言，本公开的含氮化合物可以应用于有机电致发光器件的阳极与有机电致发光层之间，以便将阳极上的空穴传输至有机电致发光层。可选的，本公开的含氮化合物可以应用于有机电致发光器件的空穴注入层、空穴传输层和电子阻挡层中的任意一层或者多层。再举例而言，本公开的含氮化合物可以应用于光电转化器件的阳极与光电转化层之间，以便将光电转化层上的空穴传输至阳极。
在本公开的一种实施方式中，所述Ar 1、Ar 2以及L的取代基分别独立地选自：氘、氰基、硝基、卤素、羟基、取代或未取代的碳原子数1-33的烷基、取代或未取代的碳原子数3-33的环烷基、取代或未取代的碳原子数2-33的烯基、取代或未取代的碳原子数2-33的炔基、取代或未取代的碳原子数2-33的杂环烷基、取代或未取代的碳原子数7-33的芳烷基、取代或未取代的碳原子数2-33的杂芳烷基、取代或未取代的碳原子数6-33的芳基、取代或未取代的碳原子数1-33的杂芳基、取代或未取代的碳原子数1-33的烷氧基、取代或未取代的碳原子数1-33的烷氨基、取代或未取代的碳原子数6-33的芳氨基、取代或未取代的碳原子数为1-33的烷硫基、取代或未取代的碳原子数7-33的芳烷氨基、取代或未取代的碳原子数1-33的杂芳氨基、取代或未取代的碳原子数为1-33的烷基甲硅烷基、取代或未取代的碳原子数为6-33的芳基甲硅烷基、取代或未取代的碳原子数为6-33的芳氧基、取代或未取代的碳原子数为6-33芳硫基。
在本公开的一种实施方式中，L选自单键、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚联苯基、取代或未取代的亚三联苯基、取代或未取代的亚芴基。
在本公开的一种实施方式中，所述含氮化合物的相对分子质量不大于750，以保证本公开的含氮化合物具有良好的热稳定性，保证本公开的含氮化合物在长时间蒸镀过程中的保持结构稳定。
在本公开的一种实施方式中，L选自单键、取代或者未取代的碳原子数为6-12的亚芳基。可选的，L选自单键或者未取代的碳原子数为6-12的亚芳基，如此，可以降低本公开的含氮化合物的制 备难度和制备成本，提高本公开的含氮化合物的在大规模应用于电子元器件时的性价比，进而降低电子元器件的成本，尤其是降低有机电致发光器件和光电转化器件的成本。
在本公开的一种实施方式中，L选自单键或者如下取代基：
Figure PCTCN2020089879-appb-000003
其中，
Figure PCTCN2020089879-appb-000004
表示化学键；*表示上述取代基用于与
Figure PCTCN2020089879-appb-000005
基团连接；**表示上述取代基用于与
Figure PCTCN2020089879-appb-000006
基团连接。
举例而言，在化合物
Figure PCTCN2020089879-appb-000007
中，L为
Figure PCTCN2020089879-appb-000008
在本公开的一种实施方式中，Ar 1和Ar 2分别独立地选自取代或者未取代的碳原子数为6-20的芳基、取代或者未取代的碳原子数为12-20的杂芳基。
在本公开的一种实施方式中，Ar 1和Ar 2分别独立地选自取代或者未取代的碳原子数为6-25的芳基，且所述Ar 1不为9,9-二苯基芴，所述Ar 2不为9,9-二苯基芴。
在本公开的一种实施方式中，Ar 1和Ar 2中的至少一个选自取代的成环碳原子数为6-12的芳基，且所述取代的成环碳原子数为6-12的芳基上的取代基选自：碳原子数为6～14的芳基、碳原子数为6～12的杂芳基。举例而言，Ar 1为
Figure PCTCN2020089879-appb-000009
则Ar 1为取代的成环碳原子数为6的芳基，且所述取代的成环碳原子数为6的芳基上的取代基为碳原子数为12的杂芳基。
在本公开的一种实施方式中，Ar 1和Ar 2分别独立地选自如下取代基：
Figure PCTCN2020089879-appb-000010
Figure PCTCN2020089879-appb-000011
在本公开的一种实施方式中，Ar 1和Ar 2分别独立地选自如下取代基：
Figure PCTCN2020089879-appb-000012
在本公开的一种实施方式中，Ar 1和Ar 2分别独立地选自如下取代基：
Figure PCTCN2020089879-appb-000013
在本公开的一种实施方式中，所述含氮化合物选自如下化合物：
Figure PCTCN2020089879-appb-000014
Figure PCTCN2020089879-appb-000015
Figure PCTCN2020089879-appb-000016
Figure PCTCN2020089879-appb-000017
Figure PCTCN2020089879-appb-000018
Figure PCTCN2020089879-appb-000019
Figure PCTCN2020089879-appb-000020
Figure PCTCN2020089879-appb-000021
Figure PCTCN2020089879-appb-000022
Figure PCTCN2020089879-appb-000023
Figure PCTCN2020089879-appb-000024
Figure PCTCN2020089879-appb-000025
Figure PCTCN2020089879-appb-000026
Figure PCTCN2020089879-appb-000027
Figure PCTCN2020089879-appb-000028
Figure PCTCN2020089879-appb-000029
Figure PCTCN2020089879-appb-000030
Figure PCTCN2020089879-appb-000031
Figure PCTCN2020089879-appb-000032
Figure PCTCN2020089879-appb-000033
Figure PCTCN2020089879-appb-000034
Figure PCTCN2020089879-appb-000035
Figure PCTCN2020089879-appb-000036
Figure PCTCN2020089879-appb-000037
Figure PCTCN2020089879-appb-000038
Figure PCTCN2020089879-appb-000039
Figure PCTCN2020089879-appb-000040
Figure PCTCN2020089879-appb-000041
本公开的含氮化合物在芴的9位引入金刚烷-2-基结构，该金刚烷基可以通过超共轭效应提升芴环以及整个含氮化合物的共轭体系的电子密度，并高了含氮化合物的空穴传导效率，进而提高了有机电 致发光器件和光电转化器件的载流子传导效率以及寿命。金刚烷-2-基引入芴的9位而非末端，进而引入本公开的含氮化合物的胺的各个侧链之间而非末端。金刚烷-2-基具有的大位阻作用，可以调节胺的各个支链之间的夹角和共轭程度，进而可以调整含氮化合物的HOMO值，使得该含氮化合物的HOMO值能够与相邻膜层更匹配，进而可以降低有机电致发光器件的驱动电压，或者提高光电转化器件的开路电压。
不仅如此，本公开的含氮化合物利用具有大体积的烷基结构对芴基团进行修饰，相较于采用芳基进行修饰，可以避免过强的π-π堆叠效应，且可以降低本公开的含氮化合物的对称性，进而可以提高含氮化合物的成膜性。不仅如此，金刚烷-2-基可以保证本公开的含氮化合物具有适宜的分子量，进而保证本公开的含氮化合物具有适宜的玻璃化转变温度，提高有机电致发光器件和光电转化器件制备时的物理和热稳定性。
本公开还提供一种有机电致发光器件。其中，如图1所示，有机电致发光器件包括相对设置的阳极100和阴极200，以及设于阳极100和阴极200之间的功能层300；功能层300包含本公开所提供的含氮化合物。
在本公开的一种实施方式中，本公开所提供的含氮化合物可以用于形成功能层300中的至少一个有机膜层，以改善有机电致发光器件性能，尤其是提高有机电致发光器件的寿命、提高有机电致发光器件的发光效率、降低有机电致发光器件的驱动电压或者提高量产的有机电致发光器件的性能均一稳定。
在本公开的一种实施方式中，功能层300包括空穴传输层320，空穴传输层320包含本公开所提供的含氮化合物。其中，空穴传输层320既可以为本公开所提供的含氮化合物组成，也可以由本公开所提供的含氮化合物和其他材料共同组成。
可选的，空穴传输层320包括第一空穴传输层321和第二空穴传输层322，且第一空穴传输层321设于第二空穴传输层322靠近阳极100的表面；第一空穴传输层321或第二空穴传输层322包含本公开所提供的含氮化合物。其中，既可以第一空穴传输层321或第二空穴传输层322中的一层包含本公开所提供的含氮化合物，也可以第一空穴传输层321和第二空穴传输层322均含有本公开所提供的含氮化合物。可以理解的是，第一空穴传输层321或第二空穴传输层322还可以含有其他材料，也可以不含有其他材料。
进一步可选的，第一空穴传输层321或第二空穴传输层322由本公开所提供的含氮化合物组成。
在本公开的一种实施方式中，功能层300包括空穴注入层310，空穴注入层310可以包含本公开提供的含氮化合物。其中，空穴注入层310既可以为本公开所提供的含氮化合物组成，也可以由本公开所提供的含氮化合物和其他材料共同组成。
可选的，空穴注入层310由本公开所提供的含氮化合物组成。
在本公开的一种实施方式中，阳极100包括以下阳极材料，其优选地是有助于空穴注入至功能层中的具有大逸出功(功函数，work function)材料。阳极材料具体实例包括：金属如镍、铂、钒、铬、铜、锌和金或它们的合金；金属氧化物如氧化锌、氧化铟、氧化铟锡(ITO)和氧化铟锌(IZO)；组合的金属和氧化物如ZnO:Al或SnO 2:Sb；或导电聚合物如聚(3-甲基噻吩)、聚[3,4-(亚乙基-1,2-二氧基)噻吩](PEDT)、聚吡咯和聚苯胺，但不限于此。优选包括包含氧化铟锡(铟锡氧化物，indium tin oxide)(ITO)作为阳极的透明电极。
在本公开的一种实施方式中，阴极200包括以下阴极材料，其是有助于电子注入至功能层中的具有小逸出功的材料。阴极材料的具体实例包括：金属如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡和铅或它们的合金；或多层材料如LiF/Al、Liq/Al、LiO 2/Al、LiF/Ca、LiF/Al和BaF 2/Ca， 但不限于此。优选包括包含铝的金属电极作为阴极。
在本公开的一种实施方式中，如图1所示，有机电致发光器件可以包括依次层叠设置的阳极100、空穴注入层310、空穴传输层320、有机电致发光层330、空穴阻挡层340、电子传输层350、电子注入层360和阴极200。其中，空穴注入层310、空穴传输层320中的至少一层包含本公开的含氮化合物。
本公开还提供一种光电转化器件，如图2所示，该光电转化器件可以包括相对设置的阳极100和阴极200，以及设于阳极100和阴极200之间的功能层300；功能层300包含本公开所提供的含氮化合物。
在本公开的一种实施方式中，本公开所提供的含氮化合物可以用于形成功能层300中的至少一个有机薄层，以改善光电转化器件性能，尤其是提高光电转化器件的寿命、提高光电转化器件的开路电压或者提高量产的光电转化器件的性能均一稳定。
在本公开的一种实施方式中，所述功能层300包括空穴传输层320，所述空穴传输层320包含本公开的含氮化合物。其中，空穴传输层320既可以为本公开所提供的含氮化合物组成，也可以由本公开所提供的含氮化合物和其他材料共同组成。
可选的，空穴传输层320还可以包括无机掺杂材料，以提高空穴传输层320的空穴传输性能。
在本公开的一种实施方式中，如图2所示，光电转化器件可包括依次层叠设置的阳极100、空穴传输层320、光电转化层370、电子传输层350和阴极200。
可选的，光电转化器件可以为太阳能电池，尤其是可以为有机薄膜太阳能电池。
化合物合成
通过如下合成路线合成化合物1-化合物23
Figure PCTCN2020089879-appb-000042
化合物1
Figure PCTCN2020089879-appb-000043
将镁条(13.54g,564mmol)和乙醚(100mL)置于氮气保护下干燥的圆底烧瓶中，加入碘(100mg)。而后将溶有2’-溴-4-氯联苯(50.00g,187.0mmol)的乙醚(200mL)溶液缓慢滴入烧瓶中，滴加完毕 后升温至35℃，搅拌3小时；将反应液降至0℃，向其中缓慢滴入溶有金刚烷酮(22.45g，149mmol)的乙醚(200mL)溶液，滴加完毕后升温至35℃，搅拌6小时；将反应液冷却至室温，向其中加入5％盐酸至pH<7，搅拌1小时，加入乙醚(200mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用乙酸乙酯/正庚烷(1:2)为流动相进行硅胶柱色谱提纯，得到白色固体中间体I-A-1(43g,收率68％)。
Figure PCTCN2020089879-appb-000044
将中间体I-A-1(43g,126.9mmol)、三氟乙酸(36.93g,380.6mmol)和二氯甲烷(300mL)加入圆底烧瓶中，氮气保护下搅拌2小时；而后向反应液中加入氢氧化钠水溶液至pH＝8，分液，有机相使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用二氯甲烷/正庚烷(1:2)进行硅胶柱色谱提纯，得到白色固体状中间体I-A(39.2g，收率96.3％)。
Figure PCTCN2020089879-appb-000045
将4-溴联苯(5.0g,21.0mmol)，4-氨基联苯(3.63g,21.45mmol)，三(二亚苄基丙酮)二钯(0.20g,0.21mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.20g,0.42mmol)以及叔丁醇钠(3.09g,32.18mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到淡黄色固体中间体II-A(5.61g,收率81.5％)。
Figure PCTCN2020089879-appb-000046
将中间体I-A(5.6g,17.46mmol)，中间体Ⅱ-A(5.61g,17.46mmol)，三(二亚苄基丙酮)二钯(0.16g,0.17mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.14g,0.35mmol)以及叔丁醇钠(2.52g,26.18mmol)加入甲苯(40mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用甲苯体系对粗品进行重结晶提纯，得到白色固体化合物1(4.35g,收率41％)。质谱：m/z＝606.3(M+H) +。 1H NMR(400MHz,CD 2Cl 2):8.09(d,1H)，7.91(s,1H),7.74-7.71(m,2H),7.61(d,4H)，7.55(d,4H),7.43(t,4H),7.37-7.30(m,3H),7.25-7.24(m,5H),7.18(dd, 1H),2.91(d,2H),2.61(d,2H),2.16(s,1H),1.90(s,3H),1.77(d,2H),1.69(d,2H),1.60(s,2H)ppm。
参照化合物1的合成方法，且使用原料2代替4-溴联苯、使用原料1代替4-氨基联苯，制备化合物2-23。其中，化合物2-化合物23的编号、结构、原料、最后一步的合成收率、表征数据等展示在表1中：
表1：化合物结构、制备及表征数据
Figure PCTCN2020089879-appb-000047
Figure PCTCN2020089879-appb-000048
Figure PCTCN2020089879-appb-000049
Figure PCTCN2020089879-appb-000050
Figure PCTCN2020089879-appb-000051
Figure PCTCN2020089879-appb-000052
其中，化合物3的氢谱为： 1H NMR(400MHz,CD 2Cl 2):8.09(d,1H),7.94(s,1H),7.90(d,1H),7.84(d,1H),7.73(t,2H),7.61(d,2H),7.56(d,2H),7.51(d,1H),7.45-7.31(m,7H),7.27-7.24(m,3H),7.20(dd,2H),2.91(d,2H),2.60(d,2H),2.15(s,1H),1.88(s,3H),1.76(d,2H),1.67(d,2H),1.60(s,2H)ppm。
其中，化合物7的氢谱为： 1H NMR(400MHz,CD 2Cl 2):8.03(d,2H),7.64(d,1H),7.58-7.57(m,2H),7.51(d,1H),7.47(d,1H),7.42-7.39(m,2H),7.36(t,2H),7.33-7.26(m,3H),7.22-7.18(m,4H),7.06(t,2H),7.01-6.99(m,2H),6.89(dd,2H),2.86(d,2H),2.43(d,2H),2.11(s,1H),1.84(s,2H),1.78(s,1H),1.71(d,2H),1.58(d,2H),1.47(s,2H),1.30(s,6H)ppm。
通过如下合成路线，合成化合物24-化合物30
Figure PCTCN2020089879-appb-000053
化合物24
Figure PCTCN2020089879-appb-000054
将中间体Ⅰ-A(20g,62.34mmol)、对氯苯硼酸(9.75g,62.34mmol)、四(三苯基膦)钯(0.72g,0.62mmol)、碳酸钾(17.2g,124.6mmol)、四丁基氯化铵(0.34g,1.25mmol)、甲苯(160mL)、乙醇(40mL)和去离子水(40mL)加入圆底烧瓶中，氮气保护下升温至78℃，搅拌8小时；将反应 液冷却至室温，加入甲苯(100mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系进行重结晶提纯，得到白色固体中间体I-A-2(18.6g，75％)。
Figure PCTCN2020089879-appb-000055
将溴苯(10.0g,38.0mmol)，4-氨基联苯(7.07g,41.8mmol)，三(二亚苄基丙酮)二钯(0.35g,0.38mmol)，2-二环己基磷-2’,4’,6’-三异丙基联苯(0.36g,0.76mmol)以及叔丁醇钠(5.48g,57.0mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到淡黄色固体中间体II-B(11.5g,86％)。
Figure PCTCN2020089879-appb-000056
将中间体I-A-2(3.50g,10.9mmol)，中间体Ⅱ-B(3.51g,10.9mmol)，三(二亚苄基丙酮)二钯(0.20g,0.22mmol)，2-二环己基磷-2’,6’-二甲氧基联苯(0.18g,0.44mmol)以及叔丁醇钠(1.58g,16.4mmol)加入甲苯(30mL)中，氮气保护下加热至105-110℃，搅拌8h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用甲苯体系对粗品进行重结晶提纯，得到白色固体化合物1(4.35g,65.81％)。质谱：m/z＝606.3(M+H) +。
参照化合物24的合成方法，并使用原料3代替4-氨基联苯，原料4代替溴苯，制备化合物25-30。其中，化合物25-化合物30的编号、结构、原料、最后一步的合成收率、表征数据等展示在表2中：
表2：化合物结构、制备及表征数据
Figure PCTCN2020089879-appb-000057
Figure PCTCN2020089879-appb-000058
化合物31
Figure PCTCN2020089879-appb-000059
将2-溴-N-苯基咔唑(10.0g,31.0mmol)、2-氨基联苯(5.78g,34.1mmol)、三(二亚苄基丙酮)二钯(0.28g,0.31mmol)、2-二环己基磷-2’,4’,6’-三异丙基联苯(0.30g,0.62mmol)以及叔丁醇钠(4.47g,46.6mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌4h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到橙色固体中间体II-C(8.65g,收率67.81％)。
Figure PCTCN2020089879-appb-000060
将中间体I-A(3.5g,10.9mmol)、中间体II-C(4.48g,10.9mmol)、三(二亚苄基丙酮)二钯(0.20g,0.22mmol)、2-二环己基磷-2’,6’-二甲氧基联苯(0.18g,0.44mmol)以及叔丁醇钠(1.57g,16.3mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌10h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过二氯甲烷/正庚烷(1/5)为流动相的硅胶柱进行色谱提纯，过柱液减压除去溶剂；使用二氯乙烷体系对粗品进行重结晶提纯，得到白色固体化合物31(5.42g,收率71.5％)。质谱：m/z＝695.3(M+H) +。
化合物32
Figure PCTCN2020089879-appb-000061
将中间体I-A(3.5g,10.9mmol)、二苯胺(1.85g,10.9mmol)、三(二亚苄基丙酮)二钯(0.20g,0.22mmol)、2-二环己基磷-2’,6’-二甲氧基联苯(0.18g,0.44mmol)以及叔丁醇钠(1.57g,16.4mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物32(3.06g,收率61.94％)。质谱：m/z＝454.2(M+H) +。
化合物33
Figure PCTCN2020089879-appb-000062
将3-溴二苯并噻吩(10.0g,38.0mmol)、4-氨基联苯(7.07g,41.8mmol)、三(二亚苄基丙酮)二钯(0.35g,0.38mmol)、2-二环己基磷-2’,4’,6’-三异丙基联苯(0.36g,0.76mmol)以及叔丁醇钠(5.48g,57.0mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌5h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到淡黄色固体中间体II-D(11.5g,收率86％)。
Figure PCTCN2020089879-appb-000063
将中间体I-A(3.5g,10.9mmol)、中间体II-D(3.83g,10.9mmol)、三(二亚苄基丙酮)二钯(0.20g,0.22mmol)、2-二环己基磷-2’,6’-二甲氧基联苯(0.18g,0.44mmol)以及叔丁醇钠(1.58g,16.4mmol)加入甲苯(30mL)中，氮气保护下加热至108℃，搅拌6h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过二氯甲烷/正庚烷(1/3)为流动相的硅胶柱进行色谱提纯，过柱液减压除去溶剂；使用甲苯体系对粗品进行重结晶提纯，得到白色固体化合物33(3.35g,收率47.5％)。质谱：m/z＝636.3(M+H) +。
化合物34
Figure PCTCN2020089879-appb-000064
将中间体I-A-2(3g,7.6mmol)、二-(4-联苯基)胺(2.43g,7.6mmol)、三(二亚苄基丙酮)二钯(0.14g,0.15mmol)、2-二环己基磷-2’,6’-二甲氧基联苯(0.12g,0.30mmol)以及叔丁醇钠(1.09g,11.33mmol)加入甲苯(25mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用甲苯体系对粗品进行重结晶提纯，得到白色固体化合物34(2.68g,收率52％)。质谱：m/z＝682.3(M+H) +。
化合物35
Figure PCTCN2020089879-appb-000065
将3-溴二苯并噻吩(10.0g,38.0mmol)、2-氨基联苯(7.07g,41.8mmol)、三(二亚苄基丙酮)二钯(0.35g,0.38mmol)、2-二环己基磷-2’,4’,6’-三异丙基联苯(0.36g,0.76mmol)以及叔丁醇钠(5.48g,57.0mmol)加入甲苯(80mL)中，氮气保护下加热至108℃，搅拌1.5h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体中间体II-F(11.5g,收率86％)。
Figure PCTCN2020089879-appb-000066
将中间体I-A-2(3.0g,7.6mmol)、中间体II-F(2.63g,7.6mmol)、三(二亚苄基丙酮)二钯(0.14g,0.15mmol)、2-二环己基磷-2’,6’-二甲氧基联苯(0.12g,0.30mmol)以及叔丁醇钠(1.09g,11.33mmol)加入甲苯(25mL)中，氮气保护下加热至108℃，搅拌3h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用甲苯体系对粗品进行重结晶提纯，得到白色固体化合物35(2.17g,收率42％)。质谱：m/z＝712.3(M+H) +。
化合物36
Figure PCTCN2020089879-appb-000067
将中间体I-A(3.0g,9.45mmol)、4-氯-1-萘硼酸(1.3g,6.30mmol)、四(三苯基膦钯)(0.15g,0.13mmol)、碳酸钾(1.74g,12.6mmol)、四丁基氯化铵(0.09g,0.31mmol)、甲苯(25mL)、乙醇(6mL)和去离子水(6mL)加入圆底烧瓶中，氮气保护下升温至78℃，搅拌16小时；将反应液冷却至室温，加入甲苯(30mL)进行萃取，合并有机相，使用无水硫酸镁进行干燥，过滤，减压除去溶剂；所得粗品使用正庚烷为流动相进行硅胶柱色谱提纯，之后用二氯甲烷/乙酸乙酯体系进行重结晶提纯，得到白色固体中间体I-A-3(1.89g，收率67％)。
Figure PCTCN2020089879-appb-000068
将中间体I-A-3(1.89g,2.91mmol)、中间体II-G(1.05g,2.91mmol)、三(二亚苄基丙酮)二钯(0.05g,0.06mmol)、2-二环己基磷-2’,6’-二甲氧基联苯(0.05g,0.12mmol)以及叔丁醇钠(0.42g,4.36mmol)加入甲苯(20mL)中，氮气保护下加热至108℃，搅拌2h；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，减压除去溶剂；使用二氯甲烷/乙酸乙酯体系对粗品进行重结晶提纯，得到白色固体化合物3836(2.05g,91％)。质谱：m/z＝772.4(M+H) +。
化合物的热稳定性
化合物在用于量产制备器件时，需要在蒸镀条件下长时间受热。若化合物在受热条件下分子结构的热稳定性差，则在长时间受热条件下化合物的纯度会下降，导致量产前中后期制备的器件性能差异较大。
本公开通过如下方法评估本公开的含氮化合物在量产蒸镀时长时间受热下分子结构的稳定性：
在高真空环境(<10 -6Pa)，以及
Figure PCTCN2020089879-appb-000069
每秒的蒸镀速度对应的温度下，对化合物1～30分别进行200小时耐热实验(保温处理)。通过耐热实验前后的纯度下降值判断本公开的含氮化合物在量产条件下的稳定性，并采用如下两个比例化合物作为对照：
Figure PCTCN2020089879-appb-000070
含氮化合物耐热实验的温度和纯度下降值结果展示在表3中：
表3 含氮化合物的试验温度和纯度下降值
Figure PCTCN2020089879-appb-000071
Figure PCTCN2020089879-appb-000072
根据表3可知，本公开的含氮化合物的纯度下降值均小于0.7％，其中绝大部分均小于0.3％。而在含有二苯基芴取代基的对比例中，纯度下降值均超过1％。因此，本公开的含氮化合物的热稳定性，远优于比较例1和比较例2。
这可能是由于含有芴-三芳基胺类型的结构在温度超过320℃时，分解速度会大幅加快。根据表3中的数据，可以推导出含氮化合物的蒸镀温度与分子量为正相关关系，320℃的蒸镀温度对应的分子量约为750。故当该含氮化合物引入大分子量的二苯基芴取代基后，很容易会使含氮化合物具有超过750的分子量，从而在同样的蒸镀速度下化合物纯度下降更多。
当化合物料纯度下降值超过1％时，会导致器件的效率和寿命发生明显降低；因此，该类热不稳定的化合物在实际量产使用中，会导致量产前中后期制备的器件性能存在较大差异。本公开中，化合物1～30的分子量均较小，从而有比较低的蒸镀温度，耐热实验证实其纯度下降值均小于0.7％，因此本公开的含氮化合物均具有优秀的量产热稳定性。
有机电致发光器件的制备和评估
实施例1
通过如下方法制备蓝色有机电致发光器件
将ITO厚度为
Figure PCTCN2020089879-appb-000073
的ITO基板(康宁制造)切割成40mm(长)×40mm(宽)×0.7mm(厚)的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极(实验基板)的功函数的和清除浮渣。
在实验基板(阳极)上真空蒸镀m-MTDATA以形成厚度为
Figure PCTCN2020089879-appb-000074
的空穴注入层(HIL)，并且在空穴注入层上真空蒸镀化合物1，以形成厚度为
Figure PCTCN2020089879-appb-000075
的第一空穴传输层。
在第一空穴传输层上蒸镀TCTA，形成厚度为
Figure PCTCN2020089879-appb-000076
的第二空穴传输层。
将α,β-ADN作为主体，按照膜厚比100:3同时掺杂BD-1，形成厚度为
Figure PCTCN2020089879-appb-000077
的发光层(EML)。
将DBimiBphen和LiQ以1:1的重量比进行混合并蒸镀形成
Figure PCTCN2020089879-appb-000078
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020089879-appb-000079
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1:9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020089879-appb-000080
的阴极。
此外，在上述阴极上蒸镀厚度为
Figure PCTCN2020089879-appb-000081
的CP-1，从而完成有机发光器件的制造。
其中，在制备电致发光器件时，所使用的各个材料的结构如下：
Figure PCTCN2020089879-appb-000082
Figure PCTCN2020089879-appb-000083
实施例2-实施例7
利用表4中所列出的第一空穴传输层材料替代实施例1中的化合物1，按照与实施例1相同的方法，制备相应的蓝色有机电致发光器件。
即，在实施例2中，利用化合物2替代化合物1制备蓝色有机电致发光器件；在实施例3中，利用化合物4替代化合物1制备蓝色有机电致发光器件；在实施例4中，利用化合物6替代化合物1制备蓝色有机电致发光器件；在实施例5中，利用化合物7替代化合物1制备蓝色有机电致发光器件；在实施例6中，利用化合物9替代化合物1制备蓝色有机电致发光器件；在实施例7中，利用化合物10替代化合物1制备蓝色有机电致发光器件。
实施例8-实施例13
利用表4中所列出的第一空穴传输层材料替代实施例1中的化合物1，利用表2中所列出的第二空穴传输层材料替代实施例1中的TCTA，按照与实施例1相同的方法，制备相应的蓝色有机电致发光器件。
即在实施例8中，利用NPB替代化合物1且利用化合物8代替TCTA制备蓝色有机电致发光器件；在实施例9中，利用NPB替代化合物1且利用化合物24代替TCTA制备蓝色有机电致发光器件；在实施例10中，利用NPB替代化合物1且利用化合物25代替TCTA制备蓝色有机电致发光器件；在实施例11中，利用NPB替代化合物1且利用化合物27代替TCTA制备蓝色有机电致发光器件；在实施 例12中，利用NPB替代化合物1且利用化合物28代替TCTA制备蓝色有机电致发光器件；在实施例13中，利用NPB替代化合物1且利用化合物29代替TCTA制备蓝色有机电致发光器件。
其中，NPB的结构如下：
Figure PCTCN2020089879-appb-000084
比较例1
利用NPB替代实施例1中的化合物1，按照与实施例1相同的方法，制备蓝色有机电致发光器件。
比较例2
利用化合物C替代实施例1中的化合物1，按照与实施例1相同的方法，制备蓝色有机电致发光器件。
其中，化合物C的结构如下：
Figure PCTCN2020089879-appb-000085
比较例3
利用NPB替代实施例1中的化合物1，利用化合物D替代实施例1中的TCTA，按照与实施例1相同的方法，制备蓝色有机电致发光器件。
其中，化合物D的结构如下：
Figure PCTCN2020089879-appb-000086
对实施例1～13和对比例1～3制备所得的蓝色有机电致发光器件，在10mA/cm 2的条件下测试了器件的IVL性能，T95器件寿命在恒定电流密度20mA/cm 2下进行测试,测试结果展示在表4中。
表4 蓝色有机电致发光器件的性能测试结果
Figure PCTCN2020089879-appb-000087
Figure PCTCN2020089879-appb-000088
根据表4可知，在色坐标CIEy相差不大的情况下，相较于比较例1和比较例2，实施例1～7所制备的蓝色有机电致发光器件具有更低的驱动电压、更高的外量子效率和更长的寿命。其中，相较于比较例1和比较例2，实施例1～7所制备的蓝色有机电致发光器件的驱动电压最大降低了9.5％，外量子效率至少提高了16.8％，T95寿命至少延长了69.5％。具体地，这对于蓝光器件而言，是非常显著的提升。
根据表4可知，在色坐标CIEy相差不大的情况下，相较于比较例1和比较例3，实施例8～13所制备的蓝色有机电致发光器件具有更低的驱动电压、更高的电流效率和外量子效率、更长的寿命。其中，相较于比较例1和比较例3，实施例8～13所制备的蓝色有机电致发光器件的驱动电压最大降低了6.4％，电流效率至少提高了21.1％，外量子效率至少提高了25％，T95寿命至少延长了69％。这对于蓝光器件而言，是非常显著的提升。
其中，外量子效率(EQE％)可以按照如下公式计算：EQE％＝射出有机电致发光器件的光子数目/注入电子数目。当然的，也可以按照如下方法计算：EQE％＝出光率*内部量子效率(出光率小于1)。对于蓝色有机电致发光器件而言，有机发光层用的是荧光材料，而荧光材料是单线态激子发光，其内部量子效率极限值为25％。而对外发光时，有机电致发光器件内部的耦合等原因将会导致光损失，因此，蓝色有机电致发光器件的外量子效率的理论极限值为25％。在理论极限值为25％的前提下，相较于比较例1和比较例2，实施例1～7所制备的蓝色有机电致发光器件的外量子效率从10.7％至少提高至12.9％，其提升幅度相对于理论极限值最高达到了17.6％，取得了非常显著的提升。在理论极限值为25％的前提下，相较于比较例1和比较例3，实施例8～13所制备的蓝色有机电致发光器件的外量子效率从 10.4％至少提高至13.5％，其提升幅度相对于理论极限值最高达到了15.9％，取得了非常显著的提升。
因此，本公开的含氮化合物用于制备有机电致发光器件时，可以有效的降低电致发光器件的驱动电压、提升外量子效率并延长有机电致发光器件的寿命。
实施例14
通过如下方法制备红色有机电致发光器件：
将ITO厚度为
Figure PCTCN2020089879-appb-000089
的ITO基板(康宁制造)切割成40mm(长)×40mm(宽)×0.7mm(高)的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极(实验基板)的功函数的和清除浮渣。
在实验基板(阳极)上真空蒸镀m-MTDATA以形成厚度为
Figure PCTCN2020089879-appb-000090
的空穴注入层(HIL)，并且在空穴注入层上蒸镀化合物11，形成厚度为
Figure PCTCN2020089879-appb-000091
的第一空穴传输层。
在第一空穴传输层上真空蒸镀化合物TPD，形成厚度为
Figure PCTCN2020089879-appb-000092
的第二空穴传输层。
在第二空穴传输层上蒸镀CBP作为主体，按照膜厚比100:3同时掺杂Ir(piq) 2(acac)，形成了厚度为
Figure PCTCN2020089879-appb-000093
的发光层(EML)。
将DBimiBphen和LiQ以1:1的重量比进行混合并蒸镀形成
Figure PCTCN2020089879-appb-000094
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020089879-appb-000095
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1：9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020089879-appb-000096
的阴极。
此外，在上述阴极上蒸镀厚度为
Figure PCTCN2020089879-appb-000097
的CP-1，形成有机覆盖层(CPL)。
其中，TPD、CBP、Ir(piq) 2(acac)的结构如下：
Figure PCTCN2020089879-appb-000098
实施例15-实施例20
利用表5中所列出的第一空穴传输层材料替代实施例14中的化合物11，按照与实施例14相同的方法，制备相应的红色有机电致发光器件。
即，在实施例15中，利用化合物12替代化合物11制备红色有机电致发光器件；在实施例16中，利用化合物13替代化合物11制备红色有机电致发光器件；在实施例17中，利用化合物14替代化合物11制备红色有机电致发光器件；在实施例18中，利用化合物18替代化合物11制备红色有机电致发光器件；在实施例19中，利用化合物19替代化合物11制备红色有机电致发光器件；在实施例20中，利用化合物20替代化合物11制备红色有机电致发光器件。
实施例21-实施例30
利用表5中所列出的第一空穴传输层材料替代实施例14中的化合物11，利用表5中所列出的第二空穴传输层材料替代实施例14中的TPD，按照与实施例14相同的方法，制备相应的红色有机电致发光器件。
即，在实施例21中，利用NPB替代化合物11且利用化合物3代替TPD制备红色有机电致发光器件；在实施例22中，利用NPB替代化合物11且利用化合物5代替TPD制备红色有机电致发光器件；在实施例23中，利用NPB替代化合物11且利用化合物15代替TPD制备红色有机电致发光器件；在实施例24中，利用NPB替代化合物11且利用化合物16代替TPD制备红色有机电致发光器件；在实施例25中，利用NPB替代化合物11且利用化合物17代替TPD制备红色有机电致发光器件；在实施例26中，利用NPB替代化合物11且利用化合物21代替TPD制备红色有机电致发光器件；在实施例27中，利用NPB替代化合物11且利用化合物22代替TPD制备红色有机电致发光器件；在实施例28中，利用NPB替代化合物11且利用化合物23代替TPD制备红色有机电致发光器件；在实施例29中，利用NPB替代化合物11且利用化合物26代替TPD制备红色有机电致发光器件；在实施例30中，利用NPB替代化合物11且利用化合物30代替TPD制备红色有机电致发光器件。
比较例4
利用NPB替代实施例14中的化合物11，按照与实施例14相同的方法，制备红色有机电致发光器件。
比较例5
利用NPB替代实施例14中的化合物11，利用化合物E替代实施例14中的TPD，按照与实施例14相同的方法，制备红色有机电致发光器件。
其中，化合物E的结构式如下：
Figure PCTCN2020089879-appb-000099
比较例6
利用NPB替代实施例14中的化合物11，利用化合物F替代实施例14中的TPD，按照与实施例14相同的方法，制备红色有机电致发光器件。
其中，化合物F的结构式如下：
Figure PCTCN2020089879-appb-000100
对如上制得的红色有机电致发光器件，在10mA/cm 2的条件下测试了器件的IVL性能，T95器件寿命在恒定电流密度20mA/cm 2下进行测试，测试结果展示在表5中。
表5 红色有机电致发光器件的性能测试结果
Figure PCTCN2020089879-appb-000101
根据表5可知，在色坐标CIEx相差不大的情况下，相较于比较例4，实施例14～20所制备的红色有机电致发光器件具有更低的驱动电压、更高的外量子效率和更长的寿命。其中，相较于比较例4，实 施例14～20所制备的红色有机电致发光器件的驱动电压至少降低了4.4％，电流效率至少提高了20.8％，外量子效率至少提高了20.5％，T95寿命至少延长了163％。
根据表5可知，在色坐标CIEx相差不大的情况下，相较于比较例5和比较例6，实施例21～30所制备的红色有机电致发光器件具有更低的驱动电压、更高的电流效率和外量子效率、更长的寿命。其中，相较于比较例5和比较例6，实施例21～30所制备的红色有机电致发光器件的驱动电压至少降低了4.6％，电流效率至少提高了16.3％，外量子效率至少提高了15.7％，T95寿命至少延长了154％。
因此，本公开的含氮化合物用于制备有机电致发光器件时，可以有效的降低电致发光器件的驱动电压、提升外量子效率并延长有机电致发光器件的寿命。
从表4和表5可知，本公开化合物用作空穴传输层材料时，能够降低有机电致发光器件的电压、提高有机电致发光器件的效率和寿命。
实施例31
通过如下方法制备蓝色有机电致发光器件
将ITO厚度为
Figure PCTCN2020089879-appb-000102
的ITO基板(康宁制造)切割成40mm(长)×40mm(宽)×0.7mm(厚)的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极(实验基板)的功函数的和清除浮渣。
在实验基板(阳极)上真空蒸镀m-MTDATA以形成厚度为
Figure PCTCN2020089879-appb-000103
的空穴注入层(HIL)，并且在空穴注入层上真空蒸镀化合物2，以形成厚度为
Figure PCTCN2020089879-appb-000104
的第一空穴传输层。
在第一空穴传输层上蒸镀TCTA，形成厚度为
Figure PCTCN2020089879-appb-000105
的第二空穴传输层。
将α,β-ADN作为主体，按照膜厚比100:3同时掺杂4,4'-(3,8-二苯基芘-1,6-二基双(N，N-二苯基苯胺)，形成厚度为
Figure PCTCN2020089879-appb-000106
的发光层(EML)。
将DBimiBphen和LiQ以1:1的重量比进行混合并蒸镀形成
Figure PCTCN2020089879-appb-000107
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020089879-appb-000108
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1:9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020089879-appb-000109
的阴极。
此外，在上述阴极上蒸镀厚度为
Figure PCTCN2020089879-appb-000110
的N-(4-(9H-咔唑-9-基)苯基)-4'-(9H-咔唑-9-基)-N-苯基-[1,1'-联苯]-4-胺。
实施例32-实施例37
利用表6中所列出的化合物替代实施例31中的化合物2，按照与实施例31相同的方法，制备相应的蓝色有机电致发光器件。
即，在实施例32中，利用化合物31替代化合物2制备蓝色有机电致发光器件；在实施例33中，利用化合物3替代化合物2制备蓝色有机电致发光器件；在实施例34中，利用化合物32替代化合物2制备蓝色有机电致发光器件；在实施例35中，利用化合物33替代化合物2制备蓝色有机电致发光器件。
比较例7-9
分别利用NPB、NPD和TPD替代实施例31中的化合物2，按照与实施例31相同的方法，制备蓝色有机电致发光器件。
其中，NPD和TPD的结构如下：
Figure PCTCN2020089879-appb-000111
对实施例31～35和对比例7～9制备所得的蓝色有机电致发光器件，在10mA/cm 2的条件下测试了器件的IVL性能，T95器件寿命在恒定电流密度20mA/cm 2下进行测试，测试结果展示在表6中。
表6 蓝色有机电致发光器件的性能测试结果
Figure PCTCN2020089879-appb-000112
根据表6可知，在色坐标CIEy相差不大的情况下，相较于比较例7～比较例9，实施例31～35所制备的蓝色有机电致发光器件具有更低的驱动电压、更高的发光效率、更高的外量子效率和更长的寿命。其中，相较于比较例7～比较例9，实施例31～35所制备的蓝色有机电致发光器件的驱动电压至少降低了5％，发光效率至少提高了17％，外量子效率至少提高了25.2％，T95寿命至少延长了67％。
因此，本公开的含氮化合物用于制备有机电致发光器件时，可以有效的降低电致发光器件的驱动电压、提升发光效率、提升外量子效率并延长有机电致发光器件的寿命。
实施例36
通过如下方法制备红色有机电致发光器件：
将ITO厚度为
Figure PCTCN2020089879-appb-000113
的ITO基板(康宁制造)切割成40mm(长)×40mm(宽)×0.7mm(高)的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极(实验基板)的功函数的和清除浮渣。
在实验基板(阳极)上真空蒸镀m-MTDATA以形成厚度为
Figure PCTCN2020089879-appb-000114
的空穴注入层(HIL)，并且在空穴注入层上蒸镀NPB，形成厚度为
Figure PCTCN2020089879-appb-000115
的第一空穴传输层。
在第一空穴传输层上真空蒸镀化合物33，形成厚度为
Figure PCTCN2020089879-appb-000116
的第二空穴传输层。
在第二空穴传输层上蒸镀CBP作为主体，按照膜厚比35:5同时掺杂Ir(piq) 2(acac)，形成了厚度为
Figure PCTCN2020089879-appb-000117
的发光层(EML)。
将DBimiBphen和LiQ以1:1的重量比进行混合并蒸镀形成
Figure PCTCN2020089879-appb-000118
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020089879-appb-000119
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1：9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020089879-appb-000120
的阴极。
此外，在上述阴极上蒸镀厚度为
Figure PCTCN2020089879-appb-000121
的N-(4-(9H-咔唑-9-基)苯基)-4'-(9H-咔唑-9-基)-N-苯基-[1,1'-联苯]-4-胺，形成有机覆盖层(CPL)。
实施例37-实施例39
利用表7中所列出的化合物替代实施例36中的化合物33，按照与实施例36相同的方法，制备相应的红色有机电致发光器件。
即，在实施例37中，利用化合物34替代化合物33制备红色有机电致发光器件；在实施例38中，利用化合物35替代化合物33制备红色有机电致发光器件；在实施例39中，利用化合物36替代化合物33制备红色有机电致发光器件。
比较例10
利用NPD替代实施例36中的化合物33，按照与实施例36相同的方法，制备红色有机电致发光器件。
比较例11
利用TPD替代实施例36中的化合物33，按照与实施例36相同的方法，制备红色有机电致发光器件。
比较例12
按照与实施例36相同的方法且不形成第二空穴传输层，制备红色有机电致发光器件。
对如上制得的红色有机电致发光器件，在10mA/cm 2的条件下测试了器件的IVL性能，T95器件寿命在恒定电流密度20mA/cm 2下进行测试，测试结果展示在表7中。
表7 红色有机电致发光器件的性能测试结果
Figure PCTCN2020089879-appb-000122
根据表7可知，在色坐标CIEx相差不大的情况下，相较于比较例10～比较例12，实施例36～39所制备的红色有机电致发光器件具有更低的驱动电压、更高的发光效率、更高的外量子效率和更长的寿命。其中，相较于比较例10～比较例12，实施例36～39所制备的红色有机电致发光器件的发光效率至少提高了20.7％，外量子效率至少提高了15.9％，T95寿命至少延长了59％。因此，本公开的含氮化合物用于制备有机电致发光器件时，可以有效的降低电致发光器件的驱动电压、提升发光效率、提升外量子效率并延长有机电致发光器件的寿命。
本公开的含氮化合物在芴的9位引入金刚烷-2-基结构，该金刚烷基可以通过超共轭效应提升芴环以及整个含氮化合物的共轭体系的电子密度，提高了含氮化合物的空穴传导效率，进而提高了有机电致发光器件和光电转化器件的载流子传导效率以及寿命。金刚烷-2-基引入芴的9位而非末端，进而引入本公开的含氮化合物的胺的各个侧链之间而非末端。金刚烷-2-基具有的大位阻作用，可以调节胺的各个支链之间的夹角和共轭程度，进而可以调整含氮化合物的HOMO值，使得该含氮化合物的HOMO值能够与相邻膜层更匹配，进而可以降低有机电致发光器件的驱动电压并提高光电转化器件的开路电压。
不仅如此，本公开的含氮化合物利用具有大体积的烷基结构对芴基团进行修饰，相较于采用芳基进行修饰，可以避免过强的π-π堆叠效应，能够提高含氮化合物的稳定性进而提高有机电致发光器件和光电转化器件的寿命。而且，通过大位阻的金刚烷-2-基对芴的9位进行修饰，可以降低本公开的含 氮化合物的对称性，进而可以降低含氮化合物的成膜性，便于有机电致发光器件和光电转化器件的制备。

Claims (18)

  1. 一种含氮化合物，其特征在于，所述含氮化合物的结构如化学式1所示：
    Figure PCTCN2020089879-appb-100001
    其中，L选自：单键、取代或未取代的碳原子数为6-30的亚芳基、取代或未取代的碳原子数为1-30的亚杂芳基；
    Ar 1和Ar 2分别独立地选自：取代或未取代的碳原子数为1-35的烷基、取代或未取代的碳原子数为2-35的烯基、取代或未取代的碳原子数为2-35的炔基、取代或未取代的碳原子数为3-35的环烷基、取代或未取代的碳原子数为2-35的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基；
    所述Ar 1、Ar 2以及L的取代基分别独立地选自：氘、氰基、硝基、卤素、羟基、取代或未取代的碳原子数1-40的烷基、取代或未取代的碳原子数3-40的环烷基、取代或未取代的碳原子数2-40的烯基、取代或未取代的碳原子数2-40的炔基、取代或未取代的碳原子数2-40的杂环烷基、取代或未取代的碳原子数7-40的芳烷基、取代或未取代的碳原子数2-40的杂芳烷基、取代或未取代的碳原子数6-40的芳基、取代或未取代的碳原子数1-40的杂芳基、取代或未取代的碳原子数1-40的烷氧基、取代或未取代的碳原子数1-40的烷氨基、取代或未取代的碳原子数6-40的芳氨基、取代或未取代的碳原子数为1-40的烷硫基、取代或未取代的碳原子数7-40的芳烷氨基、取代或未取代的碳原子数1-24的杂芳氨基、取代或未取代的碳原子数为1-45的烷基甲硅烷基、取代或未取代的碳原子数为6-50的芳基甲硅烷基、取代或未取代的碳原子数为6-30的芳氧基、取代或未取代的碳原子数为6-30芳硫基。
  2. 根据权利要求1所述的含氮化合物，其特征在于，所述Ar 1不为9,9-二苯基芴基；所述Ar 2不为9,9-二苯基芴基。
  3. 根据权利要求1或2所述的含氮化合物，其特征在于，L选自单键、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚联苯基、取代或未取代的亚三联苯基、取代或未取代的亚芴基。
  4. 根据权利要求1或2所述的含氮化合物，其特征在于，所述含氮化合物的相对分子质量不大于750。
  5. 根据权利要求1或2所述的含氮化合物，其特征在于，L选自单键、取代或者未取代的碳原子数为6-12的亚芳基。
  6. 根据权利要求1或2所述的含氮化合物，其特征在于，L选自单键或者如下取代基：
    Figure PCTCN2020089879-appb-100002
    其中，
    Figure PCTCN2020089879-appb-100003
    表示化学键；
    *表示上述取代基用于与
    Figure PCTCN2020089879-appb-100004
    基团连接；
    **表示上述取代基用于与
    Figure PCTCN2020089879-appb-100005
    基团连接。
  7. 根据权利要求1或2所述的含氮化合物，其特征在于，Ar 1和Ar 2分别独立地选自取代或者未取代的碳原子数为6-20的芳基、取代或者未取代的碳原子数为12-20的杂芳基。
  8. 根据权利要求1或2所述的含氮化合物，其特征在于，Ar 1和Ar 2中的至少一个选自取代的成环碳原子数为6-12的芳基，且所述取代的成环碳原子数为6-12的芳基上的取代基选自：碳原子数为6～14的芳基、碳原子数为6～12的杂芳基。
  9. 根据权利要求1或2所述的含氮化合物，其特征在于，Ar 1和Ar 2分别独立地选自如下取代基：
    Figure PCTCN2020089879-appb-100006
    Figure PCTCN2020089879-appb-100007
  10. 根据权利要求1或2所述的含氮化合物，其特征在于，Ar 1和Ar 2分别独立地选自如下取代基：
    Figure PCTCN2020089879-appb-100008
  11. 根据权利要求1或2所述的含氮化合物，其特征在于，所述含氮化合物选自如下化合物所形成的组：
    Figure PCTCN2020089879-appb-100009
    Figure PCTCN2020089879-appb-100010
    Figure PCTCN2020089879-appb-100011
    Figure PCTCN2020089879-appb-100012
    Figure PCTCN2020089879-appb-100013
    Figure PCTCN2020089879-appb-100014
    Figure PCTCN2020089879-appb-100015
    Figure PCTCN2020089879-appb-100016
    Figure PCTCN2020089879-appb-100017
    Figure PCTCN2020089879-appb-100018
    Figure PCTCN2020089879-appb-100019
    Figure PCTCN2020089879-appb-100020
    Figure PCTCN2020089879-appb-100021
    Figure PCTCN2020089879-appb-100022
    Figure PCTCN2020089879-appb-100023
    Figure PCTCN2020089879-appb-100024
    Figure PCTCN2020089879-appb-100025
    Figure PCTCN2020089879-appb-100026
    Figure PCTCN2020089879-appb-100027
    Figure PCTCN2020089879-appb-100028
    Figure PCTCN2020089879-appb-100029
    Figure PCTCN2020089879-appb-100030
    Figure PCTCN2020089879-appb-100031
    Figure PCTCN2020089879-appb-100032
    Figure PCTCN2020089879-appb-100033
    Figure PCTCN2020089879-appb-100034
    Figure PCTCN2020089879-appb-100035
    Figure PCTCN2020089879-appb-100036
    Figure PCTCN2020089879-appb-100037
    Figure PCTCN2020089879-appb-100038
    Figure PCTCN2020089879-appb-100039
  12. 一种有机电致发光器件，其特征在于，包括相对设置的阳极和阴极，以及设于所述阳极和所述阴极之间的功能层；
    所述功能层包含权利要求1～11任一项所述的含氮化合物。
  13. 根据权利要求12所述的有机电致发光器件，其特征在于，所述功能层包括空穴传输层，所述空穴传输层包含所述的含氮化合物。
  14. 根据权利要求12所述的有机电致发光器件，其特征在于，所述空穴传输层包括第一空穴传输层和第二空穴传输层，且所述第一空穴传输层设于所述第二空穴传输层靠近所述阳极的表面；
    所述第一空穴传输层或所述第二空穴传输层包含所述的含氮化合物。
  15. 根据权利要求12所述的有机电致发光器件，其特征在于，所述功能层包括空穴注入层，所述空穴注入层包含所述的含氮化合物。
  16. 一种光电转化器件，其特征在于，包括相对设置的阳极和阴极，以及设于所述阳极和所述阴极之间的功能层；
    所述功能层包含权利要求1～11任一项所述的含氮化合物。
  17. 根据权利要求16所述的光电转化器件，其特征在于，所述功能层包括空穴传输层，所述空穴传输层包含所述的含氮化合物。
  18. 根据权利要求16所述的光电转化器件，其特征在于，所述光电转化器件为太阳能电池。
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