WO2021073385A1 - 一种含硼类化合物及含有其的有机电致发光器件 - Google Patents

一种含硼类化合物及含有其的有机电致发光器件 Download PDF

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WO2021073385A1
WO2021073385A1 PCT/CN2020/117225 CN2020117225W WO2021073385A1 WO 2021073385 A1 WO2021073385 A1 WO 2021073385A1 CN 2020117225 W CN2020117225 W CN 2020117225W WO 2021073385 A1 WO2021073385 A1 WO 2021073385A1
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ring
compound
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魏金贝
曾礼昌
李熠烺
李国孟
徐超
孙磊
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北京鼎材科技有限公司
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Publication of WO2021073385A1 publication Critical patent/WO2021073385A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled
    • 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 a boron-containing organic material, which belongs to the technical field of organic luminescent materials.
  • the invention also relates to the application of the compound in an organic electroluminescence device.
  • OLEDs Organic electroluminescent diodes
  • the red and green dyes which are the three primary colors, generally contain heavy atoms such as Ir, Pt, etc., and theoretically can achieve 100% internal quantum efficiency, high electroluminescence efficiency, and low power consumption. They have become the current commercialization The mainstream of display devices. However, the chromaticity and lifetime of blue phosphorescent materials cannot meet the current commercial display requirements. Currently, blue light devices still use traditional fluorescent materials to achieve high color purity and long device life.
  • the rigid planar structure also causes the energy level difference between the singlet state and the triplet state to be larger, and the reverse system from the triplet state to the singlet state is slower.
  • the exciton recombines on the dye will cause serious efficiency roll-off.
  • the life span is short.
  • a rigid structure that is too flat will often cause adverse effects such as spectral broadening and red shift due to excessive doping concentration.
  • the present invention provides a new type of compound, which is a thermally activated delayed fluorescent material.
  • the structure of this series of compounds introduces arylalkyl groups to increase the molecular distance, inhibit molecular accumulation and Dexter energy transfer, thereby improving the use of the The efficiency roll-off problem of organic electroluminescent devices based on similar compounds; in addition, the arylalkyl group has an ideal anchoring effect, which can promote the arrangement of molecules parallel to the plane of the OLED substrate, which is beneficial for light extraction and enhances luminous efficiency .
  • the present invention provides a new type of boron-based organic compound, the structure of which is shown in the general formula (1):
  • Rings A, B, C, D, and E each independently represent an aromatic ring or a heteroaromatic ring, and two adjacent rings can be fused to form a five-membered ring or a six-membered ring containing X 1 or X 2;
  • ring A and ring C are fused to form a five-membered or six-membered ring containing X 1 ; alternatively, ring B and ring D are fused to form a five-membered or six-membered ring containing X 2; or, ring A and Ring C is fused to form a five-membered ring or six-membered ring containing X 1 , and at the same time, ring B and ring D are fused to form a five-membered ring or six-membered ring containing X 2;
  • X 1 and X 2 are each independently selected from one of O, S, N, C, and Si;
  • R 1 , R 2 , R 3 , R 4 , and R 5 each independently represent mono-substitution to the maximum allowable substituent, and are each independently selected from hydrogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1 ⁇ C10 alkoxy, halogen, cyano, nitro, hydroxyl, ester, silyl, amino, substituted or unsubstituted C6 ⁇ C30 arylamino, substituted or unsubstituted C3 ⁇ C30 heteroarylamino, substituted Or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or a combination of at least two, and at least one of R 1 , R 2 , R 3 , R 4 and R 5
  • One is the formula G;
  • Z 1 is selected from C or Si
  • R A , R B and R C are each independently selected from C1 ⁇ C10 chain alkyl, C3 ⁇ C10 cycloalkyl, substituted or unsubstituted C6 ⁇ C30 aryl, substituted or unsubstituted C3 ⁇ C30 heteroaryl At least one of R A , R B and R C is a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group, and at least one of the C1-C10
  • the chain alkyl group may be a C3-C10 cycloalkyl group.
  • the substituents are selected from halogen, cyano, carbonyl, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy Or a thioalkoxy group, a C6-C30 monocyclic aryl group or a condensed ring aryl group, a C3-C30 monocyclic heteroaryl group or a condensed ring heteroaryl group, or a combination of at least two of them.
  • the maximum allowable substituent refers to the maximum number of substituents on the premise that the substituted group meets the requirements of the chemical bond.
  • the expression of Ca to Cb means that the number of carbon atoms of the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituent.
  • connection site is at any position on the ring structure that can form a bond.
  • the substituted or unsubstituted C6-C30 aryl group is preferably a C6-C20 aryl group, more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, Fluorenyl and its derivatives, fluoranthene, triphenylene, pyrenyl, perylene, A group in the group consisting of a tetraphenyl group and a tetraphenyl group.
  • the biphenyl group is selected from 2-biphenyl group, 3-biphenyl group and 4-biphenyl group;
  • terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, P-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl;
  • the naphthyl group includes 1-naphthyl and 2-naphthyl; anthracenyl is selected from 1-anthryl, 2-anthryl and 9-anthryl;
  • said fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl;
  • the fluorenyl derivative is selected from 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluoren
  • the heteroatom in the present invention generally refers to an atom or group of atoms selected from N, O, S, P, Si and Se, preferably selected from N, O, and S.
  • the name of the atom in the present invention includes its corresponding isotopes.
  • hydrogen (H) includes 1 H (protium or as H), 2 H (deuterium or as D), etc.
  • carbon (C) includes 12 C, 13 C, etc.
  • the substituted or unsubstituted C3-C30 heteroaryl group is preferably a C4-C20 heteroaryl group, more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc.
  • examples include: furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and Among its derivatives, the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.
  • the above-mentioned C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, and more preferably a C1-C6 chain alkyl group.
  • Examples include methyl, ethyl, and n-propyl. , N-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, tert-butyl, etc.
  • C3-C12 cycloalkyl groups include monocyclic alkyl groups and polycyclic alkyl groups, preferably C1-C10 alkyl groups and C3-C10 cycloalkyl groups.
  • the rings A, B, C, D, and E are each independently selected from a 5- to 8-membered aryl ring or a 5- to 8-membered heteroaryl ring; preferably Yes, the rings A, B, C, D, and E are each independently selected from a 6-membered aryl ring or a 5-membered heteroaryl ring.
  • the rings A, B, C, D, and E are independently selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C3-C30 heterocycles.
  • One of the aryl groups; preferably, the rings A, B, C, D, and E are independently selected from the following substituted or unsubstituted groups: benzene ring, furan ring, thiophene ring, naphthalene ring, phenanthrene ring Ring or carbazole ring.
  • the compound of the general formula of the present invention is selected from one of the following formulas (I), (II), (III), (IV), (V), (VI), (VII) or (VIII) :
  • the compound of the general formula of the present invention is selected from the following formula (I), (II) or (III):
  • formula G is the following formula G1:
  • R A and R B is C1 ⁇ C10 chain alkyl or C3 ⁇ C10 cycloalkyl
  • R C1 is selected from hydrogen, C1 ⁇ C10 chain alkyl, C3 ⁇ C10 cycloalkyl, C1 ⁇ C10 alkane Oxygen, substituted or unsubstituted C6 ⁇ C30 arylamino, substituted or unsubstituted C3 ⁇ C30 heteroarylamino, substituted or unsubstituted C6 ⁇ C30 aryl, substituted or unsubstituted C3 ⁇ C30 heteroaryl
  • R C1 is selected from hydrogen, C1 ⁇ C10 chain alkyl, C3 ⁇ C10 cycloalkyl, C1 ⁇ C10 alkane Oxygen, substituted or unsubstituted C6 ⁇ C30 arylamino, substituted or unsubstituted C3 ⁇ C30 heteroarylamino, substituted or unsubstituted C6 ⁇ C30 aryl, substituted or unsubsti
  • R A and R B is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl , N-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl or cyclooctyl
  • R C1 is selected from hydrogen, deuterium, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenyl, naphthyl, anthryl, thienyl, pyrrolyl, indolyl, carbazolyl or pyr
  • the formula G is one of the following formulas a, b, c or d:
  • R 6 and R 7 are each independently selected from one or a combination of at least two of hydrogen, deuterium, halogen, C1-C10 chain alkyl, and C3-C10 cycloalkyl; most preferably, the formula G is selected From formula a or formula c.
  • R 6 and R 7 are each independently selected from hydrogen, or each independently selected from one of the following groups:
  • said R 6 and R 7 are each independently selected from hydrogen.
  • the R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, or each independently selected from one of the following groups:
  • an application of the above-mentioned compound in an organic electroluminescent device is preferably used as a light-emitting layer material in an organic electroluminescent device, more preferably used as a material in the light-emitting layer in the light-emitting layer of an organic electroluminescent device, and can be used as a light-emitting dye in particular.
  • an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein, the organic layer contains the compound of the general formula (1), (2) or (3) as described above, or contains the compound of the structure represented by M1-M140 or M141-M248 as described above.
  • an embodiment of the present invention provides an organic electroluminescent device, including a substrate, and a first electrode, a plurality of light-emitting functional layers, and a second electrode sequentially formed on the substrate;
  • the functional layer includes a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer.
  • the hole injection layer is formed on the anode layer, and the hole transport layer is formed on the hole.
  • the cathode layer is formed on the electron transport layer, and between the hole transport layer and the electron transport layer is a light-emitting layer; wherein, the light-emitting layer contains the above
  • the present invention also discloses a display screen or display panel, wherein the above-mentioned organic electroluminescent device is adopted in the display screen or display panel; preferably, the display screen or display panel is an OLED display.
  • the present invention also discloses an electronic device, wherein the electronic device has a display screen or a display panel, and the display screen or the display panel adopts the organic electroluminescent device as described above.
  • the OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel manufacturing enterprises for high-performance materials.
  • the boron atom contained in the compound of the present invention has a resonance effect with heteroatoms (such as nitrogen atoms) in the same ring, so this series of materials have the characteristics of narrow spectrum and thermally activated delayed fluorescence emission.
  • the series of materials of the present invention contain aryl or heteroaryl substituted quaternary carbon or quaternary silicon, etc., which can further increase the molecular distance while ensuring the transmission capacity, inhibit the quenching caused by accumulation, and further reduce the efficiency roll-off , Extend the life of the device.
  • the preparation process of the compound of the present invention is simple and feasible, and the raw materials are easily obtained, which is suitable for mass production and scale-up.
  • obtaining the compound is not limited to the synthetic methods and raw materials used in the present invention, and those skilled in the art can also select other methods or routes to obtain the compound proposed in the present invention.
  • the compounds of the synthesis method not mentioned in the present invention are all raw materials obtained through commercial channels, or they are self-made according to well-known methods through these raw materials.
  • the solvents and reagents used in the present invention can be purchased from the domestic chemical product market, for example, from Sinopharm Group Reagent Company, TCI Company, Shanghai Bi De Pharmaceutical Company, Bai Lingwei Reagent Company, etc.
  • 1,3-dibromo-5-(2-phenylpropan-2-yl)benzene (35.2g, 100mmol), diphenylamine (41.7g, 250mmol), Pd 2 (dba) 3 (0.92g, 1mmol), s-Phos (0.82g, 2mmol), sodium tert-butoxide (24g, 250mmol), and xylene (500ml) were added to a 1L single-neck flask, replaced with nitrogen three times, and heated to 130°C for overnight reaction.
  • reaction system was heated to 110°C and reacted for 12 hours.
  • the organic phase was spin-dried under reduced pressure. It was extracted three times with ethyl acetate (200ml), and the organic phases were combined and dried over anhydrous sodium sulfate.
  • the synthesis method is similar to the synthesis of M1, except that the diphenylamine is replaced with the equivalent amount of bis(4-tert-butylphenyl)amine to obtain compound M6 with a yield of 15.1%.
  • the molecule is determined by molecular mass spectrometry. Ion mass: 762.49 (theoretical value: 762.51).
  • the synthesis method is similar to that of M37, but the difference is that diphenylamine is replaced with the same amount of bis(3-tert-butylphenyl)amine to obtain compound M49 with a yield of 15.5%.
  • the molecule is determined by molecular mass spectrometry. Ion mass: 816.57 (theoretical value: 816.54).
  • 1-bromo-2,3-dichlorobenzene (22.4g, 100mmol), bis(4-(2-phenylprop-2-yl)phenyl)amine (129.7g, 320mmol), Pd 2 ( dba) 3 (2.8g, 3mmol), s-Phos (1.2g, 3mmol), sodium tert-butoxide (33.6g, 350mmol), xylene (1200ml) were added to a 2L single-neck flask, replaced with nitrogen three times, and heated to 130 React overnight at °C.
  • the synthesis method is similar to that of M55, except that 1-bromo-2,3-dichlorobenzene is replaced with the equivalent amount of 1-bromo-2,3-dichloro-5-methylbenzene to obtain the compound M66, the yield was 23.5%, and the molecular ion mass determined by molecular mass spectrometry: 906.48 (theoretical value: 906.51).
  • the synthesis method is similar to that of M89, except that 2-bromo-1,3-difluorobenzene is replaced with an equivalent amount of 2-bromo-1,3-difluoro-5-methylbenzene to obtain the compound M90, the yield was 19.6%, and the molecular ion mass determined by molecular mass spectrometry: 902.51 (theoretical value: 902.48).
  • embodiments of the present invention also provide an organic electronic light-emitting device containing the compounds of the above-mentioned embodiments.
  • OLED organic electronic light-emitting device
  • the following uses OLED as an example of an organic electronic light-emitting device as an example of the device, but it should be understood that the following detailed description is not a limit to the present invention, and those skilled in the art can extend the following detailed description to other organic electronics In the light-emitting device.
  • the OLED includes a first electrode and a second electrode, and a plurality of organic material layers between the electrodes.
  • the organic material layer can be divided into multiple regions.
  • the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.
  • a substrate may be used below the first electrode or above the second electrode.
  • the substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance, and transparency.
  • thin film transistors TFT may also be provided on the substrate used as a display.
  • the first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate.
  • transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), zinc oxide (ZnO), and any combination thereof can be used.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • SnO 2 tin dioxide
  • ZnO zinc oxide
  • magnesium (Mg) silver
  • silver (Ag) aluminum
  • Al-lithium (Al-Li) aluminum-lithium (Al-Li)
  • magnesium-silver can be used (Mg-Ag) and other metals or alloys and any combination between them.
  • the organic material layer can be formed on the electrode by methods such as vacuum thermal evaporation, spin coating, and printing.
  • the compound used as the organic material layer may be organic small molecules, organic macromolecules, and polymers, and combinations thereof.
  • the hole transport region is located between the anode and the light-emitting layer.
  • the hole transport region may be a single-layered hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds.
  • the hole transport region may also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • the material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or conductive dopant-containing polymers such as polyphenylene vinylene, polyaniline/dodecyl benzene sulfonic acid (Pani /DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly( 4-styrene sulfonate) (Pani/PSS), aromatic amine derivatives such as the following compounds HT-1 to HT-34; or any combination thereof.
  • phthalocyanine derivatives such as CuPc
  • conductive polymers or conductive dopant-containing polymers such as polyphenylene vinylene, polyaniline/dodecyl benzene sulfonic acid (Pani /
  • the hole injection layer is located between the anode and the hole transport layer.
  • the hole injection layer can be a single compound material or a combination of multiple compounds.
  • the hole injection layer may use one or more of the above-mentioned HT-1 to HT-34 compounds, or use one or more of the following HI1-HI3 compounds; it may also use HT-1 to HT-34 One or more of the compounds doped with one or more of the following HI1-HI3 compounds.
  • the light-emitting layer includes light-emitting dyes (ie, dopants) that can emit different wavelength spectra, and may also include a host material (Host) at the same time.
  • the light-emitting layer adopts fluorescent electroluminescence technology.
  • the fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-13 listed below.
  • the OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode.
  • the electron transport region can be a single-layered electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds.
  • the electron transport region may also have a multilayer structure including at least one of an electron injection layer ((EIL)), an electron transport layer ((ETL)), and a hole blocking layer ((HBL)).
  • the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-57 listed below.
  • the device may also include an electron injection layer located between the electron transport layer and the cathode.
  • the material of the electron injection layer includes but is not limited to one or a combination of the following: LiQ, LiF, NaCl, CsF, Li 2 O, Cs 2 CO 3 , BaO, Na, Li and/or Ca.
  • the device structure is as follows:
  • the preparation process of the organic electroluminescence device is as follows: the glass plate coated with a transparent conductive layer of ITO (150nm thick) is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, and degreasing ultrasonically in a mixed solvent of acetone and ethanol. Bake in a clean environment until the moisture is completely removed, clean with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam;
  • the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10nm and 40nm respectively;
  • ET-59 is vacuum-evaporated on the light-emitting layer as the electron transport layer of the organic electroluminescence device, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30nm;
  • device embodiment 2-12 and comparative example 1-2 The manufacturing process of device embodiment 2-12 and comparative example 1-2 is the same as device embodiment 1, the difference is that the dye M1 is replaced with the compound M3, M6, M14, M31, M44, M49, M55, M76, M81, M106 and M108, or replace M1 with the compounds DABAN-1 and R1 in the prior art.
  • the organic electroluminescent device prepared by the above process was tested as follows:
  • the voltage is increased at a rate of 0.1V per second, and the voltage when the brightness of the organic electroluminescent device reaches 1000cd/m 2 is measured, that is, the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density It is the current efficiency; the efficiency roll-off is the ratio of (the efficiency at the maximum brightness minus the efficiency at the specified brightness) to the maximum efficiency; the life test of LT95 is as follows: use a brightness meter to maintain a constant current at a brightness of 1000cd/m 2 Measure the time for the brightness of the organic electroluminescent device to drop to 950cd/m 2 in hours. Specific performance data are shown in Table 1 below.
  • the compound of the present invention introduces a more sterically hindered aromatic on the rigid structure.
  • the base alkyl group effectively inhibits the accumulation of molecules and the energy transfer of Dexter, and the stability of the device is improved, which is beneficial to the practical application of the compound of the present invention.

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Abstract

提供了一种有机化合物，具有如下式(1)的结构，环A、B、C、D、E分别独立地代表芳环或杂芳环，且相邻的两个环之间可稠合形成含有X 1或X 2的五元环或六元环；X 1和X 2分别独立地选自O、S、N、C、Si中的一种；m、n分别独立地为0、1或2，R 1至R 5分别独立地选自氢、C1～C10链状烷基、C3～C10环烷基、C1～C10烷氧基、卤素、氰基、硝基、羟基、酯基、硅烷基、氨基、芳基氨基、杂芳基氨基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基中的一种，且其中的至少一个为式G。所述化合物作为OLED器件中的发光层材料时，表现出优异的器件性能和稳定性。还提供了采用上述通式化合物的有机电致发光器件。

Description

一种含硼类化合物及含有其的有机电致发光器件 技术领域
本发明涉及一种含硼类有机材料，属于有机发光材料技术领域，本发明还同时涉及该化合物在有机电致发光器件中的应用。
背景技术
人们获取信息的主要途径是通过视觉来实现的，因此在人类同信息交互的过程中，显示装置至关重要。有机电致发光二极管(OLEDs)具有可柔性、自发光、高对比度、大尺寸、低功耗等诸多优点而成为了目前主流的显示装置之一。
其中作为三基色的红光以及绿光染料，由于一般含有重原子如Ir、Pt等，理论上能够实现100％的内量子效率，电致发光效率较高，功耗低，成为了目前商业化显示设备的主流。然而，蓝色磷光材料的色度以及寿命都达不到目前商业化的显示需求。目前，蓝光器件仍然采用传统荧光材料来实现高的色纯度以及长的器件寿命。
近来，日本的Takuji Hatakeyama以及Junji Kido等研究者报道了一系列基于B-N共振型的TADF(Thermally Activated Delayed Fluorescence，热活化延迟荧光)的有机材料DABNA-1(Adv.Mater.2016,28,2777–2781J.Mater.Chem.C,2019,7,3082-3089)，该类化合物硼原子、氮原子以及苯基，构成了刚性多环的芳香族骨架，因而具有较高的荧光量子产率。该类化合物与传统的蓝色荧光染料相比，光谱更窄、色纯度高优异。然而，刚性平面结构也导致了其单线态与三线态能级差较大，三线态到单线态的反向系间窜越较慢，激子在染料上复合后会引起严重的效率滚降，器件寿命较短。此外，过于平面的刚性结构往往也会导致因掺杂浓度过高导致的光谱变宽以及红移等不利影响。
Figure PCTCN2020117225-appb-000001
现有的有机电致发光材料在发光性能方面还有很大的改进余地，业界亟需开发新的发光材料体系以满足商业化需求。
发明内容
为解决上述技术问题，本发提供了一种新型化合物，属于热活化延迟荧光材料，该系列化合物结构中引入芳基烷基，增加分子间距，抑制分子堆积以及Dexter能量传递，进而改善了采用该类化合物的有机电致发光器件的效率滚降问题；此外，该芳基烷基具有较理想的锚定效应，可以促进分子采取与OLED基板平面相平行的排列，有利于光取出而提升发光效率。
本发明提供了一类基于硼的新型有机化合物，其结构如通式(1)所示：
Figure PCTCN2020117225-appb-000002
在通式(1)中：
环A、B、C、D、E分别独立地代表芳环或杂芳环，且相邻的两个环之间可稠合形成含有X 1或X 2的五元环或六元环；
优选的，环A与环C稠合形成含有X 1的五元环或六元环；或者，环B与环D稠合形成含有X 2的五元环或六元环；或者，环A与环C稠合形成含有X 1的五元环或六元环，同时，环B与环D稠合形成含有X 2的五元环或六元环；
X 1和X 2分别独立地选自O、S、N、C、Si中的一种；
m为0、1或2，当X 1选自O或S时，m为0；n为0、1或2，当X 2选自O或者S时，n为0；
R 1、R 2、R 3、R 4、R 5分别独立地表示单取代到最大允许取代基，且分别独立地选自氢、C1～C10链状烷基、C3～C10环烷基、C1～C10烷氧基、卤素、氰基、硝基、羟基、酯基、硅烷基、氨基、取代或未取代的C6～C30芳基氨基、取代或未取代的C3～C30杂芳基氨基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基中的一种或至少两种的组合，且R 1、R 2、R 3、R 4和R 5中的至少一个为式G；
在通式G中：Z 1选自C或者Si；
R A、R B、R C分别独立地选自C1～C10链状烷基、C3～C10环烷基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基中的一种，且R A、R B和R C中的至少一个为取代或未取代的C6～C30芳基或者为取代或未取代的C3～C30杂芳基，同时至少一个为C1～C10链状烷基或者为C3～C10环烷基。
当上述基团存在取代基时，所述取代基选自卤素、氰基、羰基、C1～C12的烷基、C3～C12的环烷基、C2～C10烯基、C1～C6的烷氧基或硫代烷氧基、C6～C30的单环芳基或稠环芳基、C3～C30的单环杂芳基或稠环杂芳基中的一种或者至少两种的组合。
需要说明的是，本发明中，最大允许取代基指的是所述取代基的个数为被取代基团满足化合键要求的前提下的最大取代个数。
在本说明书中，Ca～Cb的表达方式代表该基团具有的碳原子数为a～b，除非特殊说明，一般而言该碳原子数不包括取代基的碳原子数。
在本说明书中，“—”划过的环结构的表达方式，表示连接位点于该环结构上任意能够成键的位置。
在本说明书中，取代或未取代的C6～C30芳基优选为C6～C20芳基，更优选为由苯基、联苯基、三联苯基、萘基、蒽基、菲基、茚基、芴基及其衍生物、荧蒽基、三亚苯基、芘基、苝基、
Figure PCTCN2020117225-appb-000003
基和并四苯基所组成的组中的基团。具体地，联苯基选自2-联苯基、3-联苯基和4-联苯基；三联苯基包括对-三联苯基-4-基、对-三联苯基-3-基、对-三联苯基-2-基、间-三联苯基-4-基、间-三联苯基-3-基和间-三联苯基-2-基；所述萘基包括1-萘基和2-萘基；蒽基选自1-蒽基、2-蒽基和9-蒽基；所述芴基选自1-芴基、2-芴基、3-芴基、4-芴基和9-芴基；所述芴基衍生物选自9,9’-二甲基芴、9,9’-螺二芴和苯并芴；所述芘基选自1-芘基、2-芘基和4-芘基；并四苯基选自1-并四苯基、2-并四苯基和9-并四苯基。
本发明中所述的杂原子，通常指选自N、O、S、P、Si和Se中的原子或原子团，优选选自N、O、S。本发明中所述的原子名称，包括其对应的各种同位素，例如，氢(H)则包括 1H(氕或作H)、 2H(氘或作D)等；碳(C)则包括 12C、 13C等。
在本说明书中，取代或未取代的作为C3～C30杂芳基优选为C4～C20杂芳基，更优选为含氮杂芳基、含氧杂芳基、含硫杂芳基等，具体的例子可举出：呋喃基、噻吩基、吡咯基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基及其衍生物，其中，所述咔唑基衍生物优选为9-苯基咔唑、9-萘基咔唑苯并咔唑、二苯并咔唑、或吲哚并咔唑。
在本说明书中，上述C1～C20链状烷基优选为C1～C10的链状烷基，更优选为C1～C6的链状烷基，例如可举出：甲基、乙基、正丙基、正丁基、正己基、正辛基、异丙基、异丁基、叔丁基等。
在本说明书中，C3～C12环烷基包括单环烷基和多环烷基，优选为C1～C10的烷基和C3-C10的环烷基。
进一步的，本发明的通式化合物中，所述环A、B、C、D、E分别独立地选自5～8元的芳基环或者选自5～8元的杂芳基环；优选的，所述环A、B、C、D、E分别独立地选自6元芳基环或5元杂芳基环。
进一步的，本发明所述的通式化合物，所述环A、B、C、D、E分别独立地选自取代或未取代的C6～C30芳基、取代或未取代的C3～C30的杂芳基中的一种；优选的，所述环A、B、C、D、E分别独立地选自取代或未取代的下述基团：苯环、呋喃环、噻吩环、萘环、菲环或咔唑环。
进一步的，本发明的通式化合物选自下述式(2):
Figure PCTCN2020117225-appb-000004
再进一步的，本发明的通式化合物选自下述式(3)：
Figure PCTCN2020117225-appb-000005
式(3)中，环C、D、R 1、R 2、R 3、R 4、R 5、m、n的定义与在通式(1)中的定义相同，所述X 1和X 2分别独立地选自O、S或N，且X 1和X 2中至少一个为N。
更进一步的，本发明的通式化合物选自下述式(Ⅰ)、(Ⅱ)、(Ⅲ)、(Ⅳ)、(Ⅴ)、(Ⅵ)、(Ⅶ)或(Ⅷ)中的一种:
Figure PCTCN2020117225-appb-000006
最优选的，本发明的通式化合物选自下述式(Ⅰ)、(Ⅱ)或(Ⅲ)：
Figure PCTCN2020117225-appb-000007
进一步优选的，式G为下述的式G1：
Figure PCTCN2020117225-appb-000008
式G1中：
R A和R B中至少一个为C1～C10链状烷基或者为C3～C10环烷基，R C1选自氢、C1～C10链状烷基、C3～C10环烷基、C1～C10烷氧基、取代或未取代的C6～C30芳基氨基、取代或未取代的C3～C30杂芳基氨基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基中的一种；
进一步优选的，R A和R B中至少一个选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、环戊基、新戊基、正己基、环己基、新己基、正庚基、环庚基、正辛基或环辛基，R C1选自氢、氘、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、苯基、萘基、蒽基、噻吩基、吡咯基、吲哚基、咔唑基或吡啶基。
再进一步优选的，式G为下述的式a、b、c或d中的一种：
Figure PCTCN2020117225-appb-000009
其中，R 6、R 7分别独立地选自氢、氘、卤素、C1～C10链状烷基、C3～C10环烷基中的一种或至少两种的组合；最优选的，式G选自式a或式c。
进一步优选的，上述的R 6、R 7分别独立地选自氢，或者分别独立的选自以下基团之一：
Figure PCTCN2020117225-appb-000010
最优选的，所述的R 6、R 7分别独立地选自氢。
进一步优选的，本发明的通式化合物中，所述的R 1、R 2、R 3、R 4、R 5分别独立地选自氢，或者分别独立的选自以下基团之一：
Figure PCTCN2020117225-appb-000011
作为本发明涉及化合物的优选结构，可以举出以下具体化合物M1-M140及M141-M248，但不限于这些化合物：
Figure PCTCN2020117225-appb-000012
Figure PCTCN2020117225-appb-000013
Figure PCTCN2020117225-appb-000014
Figure PCTCN2020117225-appb-000015
Figure PCTCN2020117225-appb-000016
Figure PCTCN2020117225-appb-000017
Figure PCTCN2020117225-appb-000018
Figure PCTCN2020117225-appb-000019
Figure PCTCN2020117225-appb-000020
Figure PCTCN2020117225-appb-000021
Figure PCTCN2020117225-appb-000022
作为本发明的另一个方面，还提供了一种如上所述的化合物在有机电致发光器件中的应用。具体说，优选在有机电致发光器件中作为发光层材料的应用，更优选为在有机电致发光器件中的发光层中作为发光层中的材料，具体说可以应用作为发光染料。
作为本发明的又一个方面，还提供了一种有机电致发光器件，包括第一电极、第二电极和插入在所述第一电极和第二电极之间的一层或多层有机层，其中所述有机层中含有如上所述的通式(1)、(2)或(3)的化合物，或者含有如上所述的M1-M140或M141-M248所示结构的化合物。
具体而言，本发明的一个实施方案提供了一种有机电致发光器件，包括基板，以及依次形成在所述基板上的第一电极、多个发光功能层和第二电极；所述的发光功能层包括空穴注入层、空穴传输层、发光层、电子传输层，所述的空穴注入层形成在所述的阳极层上，所述的空穴传输层形成在所述的空穴注入层上，所述的阴极层形成在所述的电子传输层上，所述的空穴传输层与所述的电子传输层之间为发光层；其中，所述的发光层中含有如上所述的通式(1)、(2)或(3)的化合物，或者含有如上所述的M1-M140或M141-M248所示结构的化合物。
本发明还公开了一种显示屏或显示面板，所述显示屏或显示面板中采用如上所述的有机电致发光器件；作为优选，所述显示屏或显示面板为OLED显示器。
本发明还公开了一种电子设备，其中所述电子设备具有显示屏或显示面板，且所述显示屏或显示面板采用如上所述的有机电致发光器件。
采用本发明化合物制备的OLED器件具有低启动电压、高发光效率和更优的使用寿命，能够满足当前面板制造企业对高性能材料的要求。
上述本发明化合物用作有机电致发光器件中的发光层中作为发光染料和/或敏化剂材料性能优异的具体原因尚不明确，推测可能是以下的原因：
1、本发明的化合物所含硼原子与同一环内的杂原子(比如氮原子)具有共振效应，因而使这一系列材料具备窄光谱以及热活化延迟荧光发射的特点。
2、本发明的一系列材料中含有芳基或杂芳基取代的季碳或季硅等，能够在保证传输能力的同时，进一步增加分子间距，抑制堆积造成的淬灭，进一步降低效率滚降，延长器件寿命。
另外，本发明化合物的制备工艺简单易行，原料易得，适合于量产放大。
具体实施方式
下面将以多个合成实施例为例来详述本发明的上述新化合物的具体制备方法，但本发明的制备方法并不限于这些合成实施例。
需要说明的是，获取该化合物并不限于本发明中所用到的合成方法和原料，本领域技术人员也可以选取其它方法或路线得到本发明所提出的化合物。本发明中未提到的合成方法的化合物的都是通过商业途径获得的原料产品，或者通过这些原料产品依据公知的方法来进行自制。
本发明中所用溶剂和试剂，例如二氯甲烷、石油醚、乙醇、叔丁基本、三溴化硼、咔唑、二苯胺等化学试剂，均可以从国内化工产品市场购买，例如购买自国药集团试剂公司、TCI公司、上海毕得医药公司、百灵威试剂公司等。
下面对本发明化合物的合成方法进行简要的说明。
合成实施例
代表性合成路径：
Figure PCTCN2020117225-appb-000023
Figure PCTCN2020117225-appb-000024
本发明中的中间体和化合物的分析检测使用ABSCIEX质谱仪(4000QTRAP)。
合成例1：M1的合成
Figure PCTCN2020117225-appb-000025
中间体M1-1的合成：
室温下，将1,3-二溴-5-(2-苯丙-2-基)苯(35.2g，100mmol)，二苯胺(41.7g，250mmol)，Pd 2(dba) 3(0.92g，1mmol)，s-Phos(0.82g，2mmol)，叔丁醇钠(24g，250mmol)，二甲苯(500ml)加入至1L单口瓶中，氮气置换三次，加热至130℃反应过夜。反应液降至室温，反应体系浓缩后以二氯甲烷萃取，大量水洗，有机相干燥后浓缩进行柱层析(PE：DCM＝20:1)得到42.4g粗品，正己烷加热煮洗得到33.1g白色固体，收率62.4％。
质谱分析确定的分子离子质量：530.29(理论值：530.27)。
化合物M1的合成：
将M1-1(5.3g，10mmol)加入至250ml三口瓶中，加入对叔丁基苯(80ml)，搅拌20分钟后将反应体系降温至-20℃，之后加入15mmol叔丁基锂，维持低温继续搅拌30分钟。之后逐步升温至90℃，持续加热3h。最后将反应体系温度再次降至-20℃，氮气保护下加入三溴化硼(5.1g，20mmol)，搅拌30分钟后加入二异丙基乙基胺(13g，80mmol)。最后将反应体系加热至110℃，反应12h。反应降至室温后，将有机相减压旋干。乙酸乙酯(200ml)萃取三次，合并有机相，无水硫酸钠干燥。有机相拌硅胶浓缩，柱层析(PE：DCM＝100:1)得2.1g粗品，甲苯/正己烷重结晶得0.95g黄色固体，收率17.6％。
质谱分析确定的分子离子质量：538.22(理论值：538.26)。
合成例2：M6的合成
合成方法与M1的合成类似，不同之处在于将二苯胺替换成等物质的量的二(4-叔丁基苯基)胺，得到化合物M6，收率为15.1％，分子质谱分析确定的分子离子质量：762.49(理论值：762.51)。
合成例3：M37的合成
Figure PCTCN2020117225-appb-000026
中间体M37-1的合成：
室温下，将(1-(3,5-二溴苯基)乙烷-1,1-二苯基)二苯(41.4g，100mmol)，二(4-叔丁基苯基)胺(90.0g，320mmol)，Pd 2(dba) 3(2.8g，3mmol)，s-Phos(1.2g，3mmol)，叔丁醇钠(33.6g，350mmol)，二甲苯(1200ml)加入至2L单口瓶中，氮气置换三次，加热至130℃反应过夜。反应液降至室温，以乙酸乙酯萃取，大量水洗，有机相干燥后浓缩进行柱层析(PE：DCM＝20:1)得到66.4g白色固体，收率81.4％。
质谱分析确定的分子离子质量：816.58(理论值：816.54)。
化合物M37的合成：
将M53-1(8.2g，10mmol)加入至500ml三口瓶中，加入对叔丁基苯(150ml)，搅拌20分钟后将反应体系降温至-20℃，之后加入15mmol叔丁基锂，维持低温继续搅拌30分钟。之后逐步升温至90℃，持续加热3h。最后将反应体系温度再次降至-20℃，氮气保护下加入三溴化硼(5.1g，20mmol)，搅拌30分钟后加入二异丙基乙基胺(13g，80mmol)。最后将反应体系加热至110℃，反应12h。反应降至室温后，将有机相减压旋干。乙酸乙酯(200ml)萃取三次，合并有机相，无水硫酸钠干燥。有机相拌硅胶浓缩，柱层析(PE：DCM＝40:1)得1.9g粗品，甲苯/正己烷重结晶得1.1g黄色固体，收率13.3％。质谱分析确定的分子离子质量：824.54(理论值：824.52)。
合成例4：M49的合成
合成方法与M37的合成类似，不同之处在于将二苯胺替换成等物质的量的二(3-叔丁基苯基)胺，得到化合物M49，收率为15.5％，分子质谱分析确定的分子离子质量：816.57(理论值：816.54)。
合成例5：M55的合成
Figure PCTCN2020117225-appb-000027
中间体M55-1的合成：
室温下，将1-溴-2,3-二氯苯(22.4g，100mmol)，双(4-(2-苯丙-2-基)苯基)胺(129.7g，320mmol)，Pd 2(dba) 3(2.8g，3mmol)，s-Phos(1.2g，3mmol)，叔丁醇钠(33.6g，350mmol)，二甲苯(1200ml)加入至2L单口瓶中，氮气置换三次，加热至130℃反应过夜。反应液降至室温，以乙酸乙酯萃取，大量水洗，有机相干燥后浓缩进行柱层析(PE：DCM＝15:1)得到60.8g白色固体，收率66.2％。
质谱分析确定的分子离子质量：918.48(理论值：918.47)。
化合物M55的合成：
将M55-1(9.2g，10mmol)加入至500ml三口瓶中，加入对叔丁基苯(150ml)，搅拌20分钟后将反应体系降温至-20℃，之后加入15mmol叔丁基锂，维持低温继续搅拌30分钟。之后逐步升温至90℃，持续加热3h。最后将反应体系温度再次降至-20℃，氮气保护下加入三溴化硼(5.1g，20mmol)，搅拌30分钟后加入二异丙基乙基胺(13g，80mmol)。最后将反应体系加热至110℃，反应12h。反应降至室温后，将有机相减压旋干。乙酸乙酯(200ml)萃取三次，合并有机相，无水硫酸钠干燥。有机相拌硅胶浓缩，柱层析(PE：DCM＝40:1)得3.2g粗品，甲苯/正己烷重结晶得2.3g黄色固体，收率26.3％。质谱分析确定的分子离子质量：892.45(理论值：892.49)。
合成例6：M66的合成
合成方法与M55的合成类似，不同之处在于将1-溴-2,3-二氯苯替换成等物质的量的1-溴-2,3-二氯-5-甲基苯，得到化合物M66，收率为23.5％，分子质谱分析确定的分子离子质量：906.48(理论值：906.51)。
合成例7：M89的合成
Figure PCTCN2020117225-appb-000028
中间体M89-1的合成：
室温下向500mL单口瓶中加入3,6-二(2-苯丙-2基)咔唑(34.3g，85mmol)，2-溴-1,3-二氟苯(7.7g，40mmol)，碳酸铯(32.6g，100mmol)，N，N-二甲基甲酰胺(350ml)，氮气置换3次后，130℃加热反应过夜。反应停止后，待冷却至室温后加入500ml水搅拌10min，有大量白色固体析出，抽滤，将滤饼用乙醇煮洗2h，降温抽滤，得到白色固体产物37.4g，收率97.6％。质谱分析确定的分子离子质量：958.42(理论值：958.39)。
化合物M89的合成：
将M89-1(9.6g，10mmol)加入至500ml三口瓶中，加入对叔丁基苯(100ml)，搅拌20分钟后将反应体系降温至-20℃，之后加入15mmol叔丁基锂，维持低温继续搅拌30分钟。之后逐步升温至90℃，持续加热3h。最后将反应体系温度再次降至-20℃，氮气保护下加入三溴化硼(5.1g，20mmol)，搅拌30分钟后加入二异丙基乙基胺(13g，80mmol)。最后将反应体系加热至110℃，反应12h。反应降至室温后，将有机相减压旋干。乙酸乙酯(200ml)萃取三次，合并有机相，无水硫酸钠干燥。有机相拌硅胶浓缩，柱层析(PE：DCM＝40:1)得1.9g粗品，甲苯/正己烷重结晶得1.2g黄色固体，收率20.3％。质谱分析确定的分子离子质量：888.47(理论值：888.46)。
合成例8：M90的合成
合成方法与M89的合成类似，不同之处在于将2-溴-1,3-二氟苯替换成等物质的量的2-溴-1,3-二氟-5-甲基苯，得到化合物M90，收率为19.6％，分子质谱分析确定的分子离子质量：902.51(理论值：902.48)。
基于相同的发明构思，本发明实施例还提供一种包含上述实施例化合物的有机电子发光器件。以下采用OLED作为有机电子发光器件作为器件的一实施例进行举例说明，但应理解的是，以下细节性描述并非对本发明的限值，本领域技术人员可以将如下细节描述扩展应用到其他有机电子发光器件中。
在一实施例中，该OLED包括位于第一电极和第二电极，以及位于电极之间的若干有机材料层。该有机材料层又可以分为多个区域。比如，该有机材料层可以包括空穴传输区、发光层和电子传输区。
在具体实施例中，在第一电极下方或者第二电极上方可以使用基板。基板均为具有机械强度、热稳定性、防水性、透明度优异的玻璃或聚合物材料。此外，作为显示器用的基板上也可以带有薄膜晶体管(TFT)。
第一电极可以通过在基板上溅射或者沉积用作第一电极的材料的方式来形成。当第一电极作为阳极时，可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO 2)、氧化锌(ZnO)等氧化物透明导电材料和它们的任意组合。第一电极作为阴极时，可以采用镁(Mg)、银(Ag)、 铝(Al)、铝-锂(Al-Li)、钙(Ca)、镁-铟(Mg-In)、镁-银(Mg-Ag)等金属或合金以及它们之间的任意组合。
有机材料层可以通过真空热蒸镀、旋转涂敷、打印等方法形成于电极之上。用作有机材料层的化合物可以为有机小分子、有机大分子和聚合物，以及它们的组合。
空穴传输区位于阳极和发光层之间。空穴传输区可以为单层结构的空穴传输层(HTL)，包括只含有一种化合物的单层空穴传输层和含有多种化合物的单层空穴传输层。空穴传输区也可以为包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)中的至少一层的多层结构。
空穴传输区的材料可以选自、但不限于酞菁衍生物如CuPc、导电聚合物或含导电掺杂剂的聚合物如聚苯撑乙烯、聚苯胺/十二烷基苯磺酸(Pani/DBSA)、聚(3,4-乙撑二氧噻吩)/聚(4-苯乙烯磺酸盐)(PEDOT/PSS)、聚苯胺/樟脑磺酸(Pani/CSA)、聚苯胺/聚(4-苯乙烯磺酸盐)(Pani/PSS)、芳香胺衍生物如下面HT-1至HT-34所示的化合物；或者其任意组合。
Figure PCTCN2020117225-appb-000029
Figure PCTCN2020117225-appb-000030
空穴注入层位于阳极和空穴传输层之间。空穴注入层可以是单一化合物材料，也可以是多种化合物的组合。例如，空穴注入层可以采用上述HT-1至HT-34的一种或多种化合物，或者采用下述HI1-HI3中的一种或多种化合物；也可以采用HT-1至HT-34的一种或多种化合物掺杂下述HI1-HI3中的一种或多种化合物。
Figure PCTCN2020117225-appb-000031
发光层包括可以发射不同波长光谱的发光染料(即掺杂剂，dopant)，还可以同时包括主体材料(Host)。在本发明的一方面，发光层采用荧光电致发光的技术。其发光层荧光主体材料可以选自、但不限于以下所罗列的BFH-1至BFH-13的一种或多种的组合。
Figure PCTCN2020117225-appb-000032
OLED有机材料层还可以包括发光层与阴极之间的电子传输区。电子传输区可以为单层结构的电子传输层(ETL)，包括只含有一种化合物的单层电子传输层和含有多种化合物的单层电子传输层。电子传输区也可以为包括电子注入层((EIL))、电子传输层((ETL))、空穴阻挡层((HBL))中的至少一层的多层结构。
在一具体示例中，电子传输层材料可以选自但不限于以下所罗列的ET-1至ET-57的一种或多种的组合。
Figure PCTCN2020117225-appb-000033
Figure PCTCN2020117225-appb-000034
Figure PCTCN2020117225-appb-000035
Figure PCTCN2020117225-appb-000036
一示例中，器件中还可以包括位于电子传输层与阴极之间的电子注入层，电子注入层材料包括但不限于以下罗列的一种或多种的组合：LiQ、LiF、NaCl、CsF、Li 2O、Cs 2CO 3、BaO、Na、Li和/或Ca。
器件实施例1
实施例1中，器件结构如下所示：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/BFH-4:M1(30nm，5wt％)/ET-59(30nm)/LiF(1nm)/Al(150nm)。
有机电致发光器件制备过程如下：将涂布了ITO(厚度150nm)透明导电层的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮：乙醇混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；
把上述带有阳极的玻璃基片置于真空腔内，抽真空至1×10 -5～1×10 -4Pa，在上述阳极层膜上真空蒸镀HI-2和HT-2分别作为空穴注入层和空穴传输层，蒸镀速率为0.1nm/s，蒸镀膜厚分别为10nm和40nm；
在空穴传输层之上真空蒸镀“BFH-4：M1(30nm，5％wt)”作为有机电致发光器件的发光层，蒸镀速率为0.1nm/s，蒸镀总膜厚为30nm；其中“5％wt”是指染料的掺杂比例，即主体材料与M1的质量份比为95:5。
在发光层之上真空蒸镀ET-59作为有机电致发光器件的电子传输层，其蒸镀速率为0.1nm/s，蒸镀总膜厚为30nm；
在电子传输层上真空蒸镀0.5nm的LiF作为电子注入层和150nm的Al作为阴极。
器件实施例2-12和对比例1-2的制作过程同器件实施例1，区别是将染料M1换为本发明的化合物M3、M6、M14、M31、M44、M49、M55、M76、M81、M106和M108，或者将M1替换为现有技术中的化合物DABAN-1和R1。
Figure PCTCN2020117225-appb-000037
对由上述过程制备的有机电致发光器件进行如下性能测定：
在同样亮度下，使用数字源表及亮度计测定实施例1～12以及对比例1-2中制备得到的有机电致发光器件的驱动电压、电流效率以及器件的寿命。具体而言，以每秒0.1V的速率提升电压，测定当有机电致发光器件的亮度达到1000cd/m 2时的电压即驱动电压，同时测出此时的电流密度；亮度与电流密度的比值即为电流效率；效率滚降为(最大亮度下的效率减去指定亮度下的效率)与最大效率的比值；LT95的寿命测试如下：使用亮度计在1000cd/m 2亮度下，保持恒定的电流，测量有机电致发光器件的亮度降为950cd/m 2的时间，单位为小时。具体性能数据详见下表1。
表1
Figure PCTCN2020117225-appb-000038
Figure PCTCN2020117225-appb-000039
Figure PCTCN2020117225-appb-000040
由上表1可以看到，采用本发明的化合物作为染料时，相比对比例采用现有技术中的化合物DABAN-1和R1，采用本发明的化合物的器件的寿命显著提升，同时发光效率也相对较高，效率滚降降低，表现出优异的器件性能。这是由于现有技术中的化合物DABAN-1过于平面，堆积密集而引起淬灭严重，进而效率较低，器件滚降严重。而R1中的B对位的三个苯环的空间位阻过高，导致载流子传输性能较差进而导致器件效率的降低，而本发明化合物在刚性结构上引入了位阻较大的芳基烷基，有效地抑制了分子的堆积以及Dexter能量传递，器件的稳定性得以提升，这有利于本发明化合物的实用化应用。
尽管结合实施例对本发明进行了说明，但本发明并不局限于上述实施例，应当理解，在本发明构思的引导下，本领域技术人员可进行各种修改和改进，所附权利要求概括了本发明的范围。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (14)

  1. 一种通式化合物，如下式(1)所示：
    Figure PCTCN2020117225-appb-100001
    式(1)中：
    环A、B、C、D、E分别独立地代表芳环或杂芳环，且相邻的两个环之间可稠合形成含有X 1或X 2的五元环或六元环；
    优选的，环A与环C稠合形成含有X 1的五元环或六元环；或者，环B与环D稠合形成含有X 2的五元环或六元环；或者，环A与环C稠合形成含有X 1的五元环或六元环，同时，环B与环D稠合形成含有X 2的五元环或六元环；
    X 1和X 2分别独立地选自O、S、N、C、Si中的一种；
    m为0、1或2，当X 1选自O或S时，m为0；n为0、1或2，当X 2选自O或者S时，n为0；
    R 1、R 2、R 3、R 4、R 5分别独立地表示单取代到最大允许取代基，且分别独立地选自氢、C1～C10链状烷基、C3～C10环烷基、C1～C10烷氧基、卤素、氰基、硝基、羟基、酯基、硅烷基、氨基、取代或未取代的C6～C30芳基氨基、取代或未取代的C3～C30杂芳基氨基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基和式G表示的基团中的一种或至少两种的组合，且R 1、R 2、R 3、R 4和R 5中的至少一个为所述式G；
    所述式G中：
    Z 1选自C或者Si；
    R A、R B、R C分别独立地选自C1～C10链状烷基、C3～C10环烷基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基中的一种，且R A、R B和R C中的至少一个为取代或未取代的C6～C30芳基或者为取代或未取代的C3～C30杂芳基，同时至少一个为C1～C10链状烷基或者为C3～C10环烷基；
    当上述基团存在取代基时，所述取代基选自卤素、氰基、羰基、C1～C12的烷基、C3～C12的环烷基、C2～C10烯基、C1～C6的烷氧基或硫代烷氧基、C6～C30的单环芳基或稠环芳基、C3～C30的单环杂芳基或稠环杂芳基中的一种或者至少两种的组合。
  2. 根据权利要求1所述的通式化合物，其中，所述环A、B、C、D、E分别独立地选自5～8元的芳基环或者选自5～8元的杂芳基环；
    优选的，所述环A、B、C、D、E分别独立地选自6元芳基环或5元杂芳基环。
  3. 根据权利要求1所述的通式化合物，其中，所述环A、B、C、D、E分别独立地选自取代或未取代的C6～C30芳基、取代或未取代的C3～C30的杂芳基中的一种；
    优选的，所述环A、B、C、D、E分别独立地选自取代或未取代的下述基团：苯环、呋喃环、噻吩环、萘环、菲环或咔唑环。
  4. 根据权利要求1所述的通式化合物，其中，所述通式化合物如下式(2)所示:
    Figure PCTCN2020117225-appb-100002
    式(2)中，环C、D、X 1、X 2、R 1、R 2、R 3、R 4、R 5、m、n的定义与在通式(1)中的定义相同。
  5. 根据权利要求1或4所述的通式化合物，其中，所述通式化合物如下式(3)所示：
    Figure PCTCN2020117225-appb-100003
    Figure PCTCN2020117225-appb-100004
    式(3)中，环C、D、R 1、R 2、R 3、R 4、R 5、m、n的定义与在通式(1)中的定义相同，所述X 1和X 2分别独立地选自O、S或N，且X 1和X 2中至少一个为N。
  6. 根据权利要求1或5所述的通式化合物，其中，所述通式化合物如下式(Ⅰ)、(Ⅱ)、(Ⅲ)、(Ⅳ)、(Ⅴ)、(Ⅵ)、(Ⅶ)或(Ⅷ)中的一种所示:
    Figure PCTCN2020117225-appb-100005
    其中，R 1、R 2、R 3、R 4、R 5的定义与在通式(1)中的定义相同。
  7. 根据权利要求1或5所述的通式化合物，其中，所述通式化合物如下式(Ⅰ)、(Ⅱ)或(Ⅲ)中的一种所示:
    Figure PCTCN2020117225-appb-100006
    其中，R 1、R 2、R 3、R 4、R 5的定义与在通式(1)中的定义相同。
  8. 根据权利要求1-7中任一所述的通式化合物，其中，所述式G为下述的式G1：
    Figure PCTCN2020117225-appb-100007
    式G1中：
    R A和R B中至少一个为C1～C10链状烷基或者为C3～C10环烷基，
    R C1选自氢、C1～C10链状烷基、C3～C10环烷基、C1～C10烷氧基、取代或未取代的C6～C30芳基氨基、取代或未取代的C3～C30杂芳基氨基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基中的一种；
    优选的，R A和R B中至少一个选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、环戊基、新戊基、正己基、环己基、新己基、正庚基、环庚基、正辛基或环辛基，R C1选自氢、氘、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、苯基、萘基、蒽基、噻吩基、吡咯基、吲哚基、咔唑基或吡啶基。
  9. 根据权利要求1-8中任一所述的通式化合物，其中，所述G为下述的式a、b、c或d中的一种：
    Figure PCTCN2020117225-appb-100008
    其中，R 6、R 7分别独立地选自氢、氘、卤素、C1～C10链状烷基、C3～C10环烷基中的一种或至少两种的组合；
    优选的，式G选自式a或式c。
  10. 根据权利要求9所述的通式化合物，其中，所述的R 6、R 7分别独立地选自氢，或者分别独立的选自以下基团之一：
    Figure PCTCN2020117225-appb-100009
    优选的，所述的R 6、R 7分别独立地选自氢。
  11. 根据权利要求1-9中任一所述的通式化合物，其中，所述的R 1、R 2、R 3、R 4、R 5分别独立地选自氢，或者分别独立的选自以下基团之一：
    Figure PCTCN2020117225-appb-100010
  12. 根据权利要求1所述的通式化合物，其中，所述通式化合物选自下述具体结构化合物：
    Figure PCTCN2020117225-appb-100011
    Figure PCTCN2020117225-appb-100012
    Figure PCTCN2020117225-appb-100013
    Figure PCTCN2020117225-appb-100014
    Figure PCTCN2020117225-appb-100015
    Figure PCTCN2020117225-appb-100016
    Figure PCTCN2020117225-appb-100017
    Figure PCTCN2020117225-appb-100018
    Figure PCTCN2020117225-appb-100019
    Figure PCTCN2020117225-appb-100020
    Figure PCTCN2020117225-appb-100021
  13. 权利要求1-12中任一所述的化合物的应用，所述应用为在有机电致发光器件中作为发光层材料。
  14. 一种有机电致发光器件，该器件包括第一电极、第二电极和插入所述第一电极和第二电极之间的一层或多层有机层，其特征在于，所述有机层中包括至少一种由权利要求1-12中任一所述的化合物；
    优选的，所述的有机功能层包括空穴注入层、空穴传输层、发光层、电子传输层，所述的空穴注入层形成在所述的阳极层上，所述的空穴传输层形成在所述的空穴注入层上，所述的阴极层形成在所述的电子传输层上，所述的空穴传输层与所述的电子传输层之间为发光层，其中，所述的发光层中含有权利要求1-12中任一所述的化合物。
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