WO2015090177A1 - 一种有机电致发光器件及其制备方法 - Google Patents

一种有机电致发光器件及其制备方法 Download PDF

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WO2015090177A1
WO2015090177A1 PCT/CN2014/093904 CN2014093904W WO2015090177A1 WO 2015090177 A1 WO2015090177 A1 WO 2015090177A1 CN 2014093904 W CN2014093904 W CN 2014093904W WO 2015090177 A1 WO2015090177 A1 WO 2015090177A1
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organic electroluminescent
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electroluminescent device
phenyl
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PCT/CN2014/093904
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French (fr)
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邱勇
段炼
张东东
张国辉
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北京维信诺科技有限公司
清华大学
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Priority to EP14872476.8A priority Critical patent/EP3070757B1/en
Priority to JP2016539984A priority patent/JP6581585B2/ja
Priority to US15/106,209 priority patent/US10312453B2/en
Priority to KR1020167018945A priority patent/KR101930146B1/ko
Publication of WO2015090177A1 publication Critical patent/WO2015090177A1/zh

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Definitions

  • the invention belongs to the field of organic electroluminescent devices, and in particular relates to an organic electroluminescent device and a preparation method thereof.
  • organic electroluminescent devices Under electro-excitation conditions, organic electroluminescent devices produce 25% singlet and 75% triplet.
  • Conventional fluorescent materials can only utilize 25% of singlet excitons due to spin-forbidden, so the external quantum efficiency is limited to only 5%. Almost all triplet excitons can only be lost by heat. In order to improve the efficiency of the organic electroluminescent device, it is necessary to make full use of triplet excitons.
  • the present invention provides a novel organic electroluminescent device and a method of preparing the same.
  • the present invention provides a novel light emitting layer of the organic electroluminescent device, and the host material in the light emitting layer is Specific materials that have charge transfer transitions.
  • the present invention also provides an organic electroluminescent device comprising the above-described light-emitting layer, comprising an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode stacked on each other.
  • the present invention also provides a method of preparing the organic electroluminescent device, comprising sequentially depositing an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode stacked on each other on a substrate, and then packaging, wherein the host material in the light-emitting layer of the host material in the light-emitting layer is a specific material having a charge transfer transition.
  • the singlet and triplet states of the material can be divided into a singlet state of the CT state, a singlet state of the (n- ⁇ ) state, a triplet state of the CT state, and a triplet state of the (n- ⁇ ) state transition.
  • the energy level of the CT excited state is often higher than the (n- ⁇ ) excited state.
  • the triplet state of the CT excited state is higher than the triplet state of the (n- ⁇ ) excited state.
  • the energy level difference between the two can be specifically described by electron volts (eV). According to the difference in material structure, it can be divided into three cases. The first one is that the difference between the two is small, such as 0-0.3eV, the other is very different, such as 1.0eV or more, and the third is The difference between the two is between the first two.
  • the material we selected is: a material with a small difference (0-0.3 eV) between the triplet state of the CT excited state and the (n- ⁇ ) excited state; or, the difference between the two is large ( >1.0eV), but the second triplet state of the (n- ⁇ ) excited state is slightly smaller or slightly higher than the material of the first singlet state of the CT excited state (the difference between the two is 0-0.1 eV).
  • the material level structure is shown in Figure 1 and Figure 2:
  • the first three-line state of the (n- ⁇ ) excited state is slightly smaller than the first three-wire state of the CT excited state (0-0.3 eV), and thus transitions to high energy in the case of absorbing external heat.
  • the first triplet state of the CT excited state returns from the first triplet state to the first singlet state of the CT excited state, thereby transmitting to the dye luminescence.
  • the triplet of the host material is fully utilized.
  • the CT state can be obtained in a compound having both a donor group and an acceptor group. Spatially separated HOMO and LUMO levels can be obtained due to spatially separated donors and acceptors.
  • the difference between the triplet state and the singlet state of the CT state is proportional to the overlap of HOMO and LUMO. Therefore, the separated HOMO and LUMO energy levels can obtain the energy difference between the singlet state and the triplet state of the small CT state, and the energy level difference is generally smaller than 0.3eV.
  • the design of such a material can achieve spatial separation by introducing a large volume of donor groups (such as carbazolyl) or acceptor groups such that the material is somewhat distorted; or by introducing a space-distorting linking group. For example, a spiro group is used to separate the donor group from the acceptor group.
  • the first triplet state of the (n- ⁇ ) excited state is much smaller than the first triplet state of the CT excited state (>1.0 eV), so under electro-excitation, (n- ⁇ )
  • the first triplet state of the excited state is rarely generated, mainly producing the second triplet state of the (n- ⁇ ) excited state, and the second triplet state energy can be transferred to the first singlet state of the CT excited state, thereby also transmitting to the dye luminescence , achieving 100% luminous efficiency.
  • This material has both local and CT states.
  • the singlet and triplet states of the local state of the material are very different, making the single-line to triplet inter-systems more difficult.
  • the singlet state energy difference between the triplet state and the local state of the CT state of the material is small, thereby making the material
  • the CT state triplet can be transferred to a singlet state. To obtain this function, it is necessary to obtain a space-distorted material, and both the donor group and the acceptor group are present to obtain the CT state, and at the same time, the local singlet state of the donor group (or acceptor group) is required. It is very different from the triplet.
  • the singlet and triplet energy levels of phenamimidazolyl, naphthylthiazolyl, benzothiazolyl or fluorenyl are above 1.0 eV, and this material is a receptor group, so the binding is bound
  • the donor group can obtain this effect of the compound.
  • the organic electroluminescent device comprises an anode, a hole transporting layer, a light emitting layer, an electron transporting layer and a cathode stacked on each other, and the light emitting layer comprises a host material and a luminescent dye, wherein
  • the host material of the luminescent layer is a material in which the triplet state of the CT excited state is higher than the triplet state of the n- ⁇ excited state, and the difference is between 0 and 0.3 eV;
  • the host material of the luminescent layer is a triplet energy level in which the CT excited state is higher than the n- ⁇ excited state, and the difference is 1.0 eV or more, and the n- ⁇ excited state of the host material is The difference between the first singlet state level of the second triplet energy level and the CT excited state is -0.1 to 0.1 eV;
  • the luminescent dye is a fluorescent dye.
  • the singlet energy level of the fluorescent dye is lower than the singlet energy level of the host material.
  • the host material is a material having a charge transfer transition, and a donor group unit and a acceptor group unit are simultaneously present in the host material.
  • the donor group unit is a group consisting of one donor group or two or more donor groups
  • the acceptor group unit is a group consisting of one acceptor group or two or more acceptor groups
  • the donor group is selected from the group consisting of an indolocarbazolyl, oxazolyl, dioxazolyl, triphenylamine, phenoxazinyl, C1-6 alkyl, methoxy, ethoxy or benzene
  • An indolozolyl group substituted with one or more groups in the group a carbazolyl group substituted with one or more groups of a C 1-6 alkyl group, a methoxy group, an ethoxy group or a phenyl group, C 1 -6 alkyl, methoxy, ethoxy or phenyl substituted with one or more groups biphenyl carbazolyl group, C 1-6 alkyl group, a methoxy group, an ethoxy group or a phenyl a group of substituted triphenylamine groups, or a C 1-6 alkyl, methoxy, ethoxy or phenyl group substituted with one or more groups;
  • the acceptor group is selected from the group consisting of naphthyl, anthracenyl, phenanthryl, anthracenyl, triazinyl, benzimidazolyl, cyano, pyridyl, sulfone, phenamimidazolyl, naphthylthiazolyl, benzo a thiazolyl group, an oxadiazolyl group, a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group substituted with one or more groups of naphthyl groups, a C 1-6 alkyl group, A a mercapto group substituted with one or more groups of an oxy group, an ethoxy group, a phenyl group or a pyridyl group, one or more of a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl
  • a substituted phenanthryl group a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group substituted with one or more groups, a C 1-6 alkyl group, a methoxy group a triazinyl group substituted with one or more groups of a group, an ethoxy group, a phenyl group or a pyridyl group, one or more of a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group.
  • a substituted benzimidazolyl group a pyridyl group substituted with one or more groups of a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group, a C 1-6 alkyl group, More than one group of methoxy, ethoxy, phenyl or pyridyl groups
  • one or more of the donor group units are directly joined to one or more of the acceptor group units to form a host material; or one or more of the donor group units and one Or a plurality of said acceptor group units are each attached to a linking group to form a host material, said linking group being a sterically hindered group.
  • one or two donor group units and one or two acceptor group units are respectively linked to a linking group to form a host material, or one or two acceptor group units and one or two The donor group units are directly joined to form a host material.
  • the linking group is selected from the group consisting of spiro fluorenyl, phenyl, biphenyl, C 1-6 alkyl or phenyl wherein at least one substituted spiro group, C 1-6 alkyl or a biphenyl group in which at least one of a phenyl group substituted with a phenyl group or a C 1-6 alkyl group or a phenyl group is substituted.
  • the donor group is selected from the group consisting of
  • the acceptor group is selected from the group consisting of:
  • the host material has the following structure:
  • the luminescent dye is a fluorescent dye having a triplet energy level of less than 2.3 eV. More preferably, the fluorescent dye is selected from the group consisting of coumarins or dipyrans.
  • the fluorescent dye has a doping concentration in the light-emitting layer of not more than 5% by weight. Further preferably, the fluorescent dye has a doping concentration in the light-emitting layer of from 0.001% by weight to 1% by weight. More preferably, the fluorescent dye has a doping concentration in the light-emitting layer of from 0.1% by weight to 1% by weight.
  • the material of the hole transport layer has a triplet energy level higher than the triplet energy level of the host material. Further preferably, the material of the hole transport layer has a triplet energy level higher than 2.5 eV. More preferably, empty
  • the material of the hole transport layer is an aromatic amine and/or dendrite low molecular material, most preferably N, N'-diphenyl-N, N'-(1-naphthyl)-1, 1'-linked. Benzene-4,4'-diamine.
  • the material of the electron transport layer has a triplet energy level higher than 2.5 eV.
  • a hole injection layer is further provided between the anode and the hole transport layer.
  • the material of the hole injection layer is 4,4′,4”-tris(3-methylphenylaniline)triphenylamine doped F4TCNQ, or copper phthalocyanine, or metal oxides such as molybdenum oxide, oxidation rhenium.
  • the present invention provides a method of preparing the above organic electroluminescent device, comprising sequentially depositing an anode, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode stacked on each other on a substrate, and then packaging.
  • the organic electroluminescent device of the present invention utilizes a novel luminescent layer host material which contains a donor group and an acceptor group, and can fully utilize the triplet state generated in the luminescent layer to achieve 100% of the fluorescent device.
  • the luminous efficiency and the elimination of precious metals eliminates the cost.
  • Figure 1 Schematic diagram of energy transfer and illumination of a light-emitting layer of a first type of material organic electroluminescent device
  • Figure 2 Schematic diagram of energy transmission and luminescence of the luminescent layer of the second type of material organic electroluminescent device
  • FIG. 3 is a schematic view showing the basic structure of an organic electroluminescent device of the present invention.
  • 07 is an electron transport layer.
  • the organic electroluminescent device of the present invention comprises an anode, a hole transporting layer, a light emitting layer, an electron transporting layer and a cathode stacked on each other, wherein the host material in the light emitting layer is a triplet state and (n- ⁇ ) excitation of a CT excited state.
  • the material of the triplet state has a small difference (0 ⁇ 0.3eV) and the difference between the two is very large ( ⁇ 1.0eV) but the second triplet state of the (n- ⁇ ) excited state is slightly smaller or slightly higher than the material of the first singlet state of the CT excited state (the difference between the two is 0 to 0.1 eV).
  • the materials selected or designed herein have spatially separated donor groups and acceptor groups in space, resulting in spatial separation of HOMO and LUMO energy levels, reducing overlap integrals, and thus CT states of materials.
  • the difference between the energy levels of the singlet and triplet states is small.
  • the singlet and triplet energy levels of the selected phenamimidazolyl, naphthylthiazolyl, benzothiazolyl or fluorenyl groups are above 1.0 eV, which can also meet the requirements of the second type of materials.
  • the host material is doped with a fluorescent dye, and the singlet state level of the fluorescent dye is lower than the CT state singlet level of the host material.
  • the luminescent dye selected has a longer illuminating wavelength than the luminescent wavelength of the host material, thereby ensuring that the singlet state of the dye is less than the singlet level of the host material.
  • the concentration of the fluorescent dye is preferably less than 1% by mass, and preferably the material having a large overlap between the absorption spectrum of the fluorescent dye and the emission spectrum of the main body is advantageous for improving the efficiency of energy transfer, and at the same time, reducing the short-range Dexter energy transfer, because this part is lost. Drop the excitons.
  • the triplet energy level of the electron and hole transporting materials in the present invention is higher than the triplet energy level of the host material, which is advantageous for limiting the excitons of the light emitting layer.
  • the triplet energy level of the fluorescent dye of the present invention is less than 2.3 eV, and the triplet level of electrons and holes is higher than 2.5 eV, so that excitons in the light-emitting layer can be effectively limited.
  • the luminescent layer of the organic electroluminescent device of the present invention comprises a host material and a luminescent dye, the host material being a material having a charge transfer transition in which both a donor group unit and a acceptor group unit are present.
  • the donor group unit is a group consisting of one donor group or two or more donor groups; the acceptor group unit is an acceptor group or two or more acceptor groups are linked to form Group
  • the structure of the host material may be a donor-connection-acceptor or a structure of a donor-acceptor-donor.
  • the donor group is selected from the group consisting of indolocarbazolyl, oxazolyl, bisoxazolyl, triphenylamine, phenoxazinyl, C1-6 alkyl, methoxy, ethoxy or phenyl
  • An oxazolyl group substituted with one or more groups an alkyl group substituted with one or more groups of a C 1-6 alkyl group, a methoxy group, an ethoxy group or a phenyl group, C 1- alkyl, a 6-methoxy group, an ethoxy group or a phenyl group substituted with one or more dibenzofuranyl group, C 1-6 alkyl group, a methoxy group, an ethoxy group or a phenyl a group of substituted triphenylamine groups, or a C 1-6 alkyl, methoxy, ethoxy or phenyl group substituted with one or more groups;
  • the acceptor group is selected from the group consisting of naphthyl, anthracenyl, phenanthryl, anthryl, triazinyl, benzimidazolyl, cyano, pyridyl, sulfone, phenamimidazolyl, naphthylthiazolyl, benzothiazolyl , a oxadiazolyl group, a naphthyl group substituted with one or more groups of a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group, a C 1-6 alkyl group, a methoxy group a mercapto group substituted with one or more groups of an ethoxy group, a phenyl group or a pyridyl group, or a group of at least one of a C1-6 alkyl group, a methoxy group, an ethoxy group, a pheny
  • a substituted phenanthryl group a fluorenyl group substituted with one or more groups of a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group, a C 1-6 alkyl group, a methoxy group, a triazinyl group substituted with one or more groups of an ethoxy group, a phenyl group or a pyridyl group, or a group of at least one of a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group.
  • a substituted benzimidazolyl group a pyridyl group substituted with one or more groups of a C 1-6 alkyl group, a methoxy group, an ethoxy group, a phenyl group or a pyridyl group, a C 1-6 alkyl group, a methoxy group Substituted with more than one of the group of ethoxy, phenyl or pyridyl Group, an alkyl group, a methoxy group, an ethoxy group, a C1-6 phenyl or pyridyl groups are substituted with one or more of phenanthroimidazolyl; C 1-6 alkyl, methoxy, ethoxy a naphthothiazole group substituted with one or more groups of a phenyl group or a pyridyl group, substituted with one or more groups of a C 1-6 alkyl group, a methoxy group, an ethoxy group
  • one or more of the donor group units are directly joined to one or more of the acceptor group units to form a host material; or one or more of the donor group units and one Or a plurality of said acceptor group units are each attached to a linking group to form a host material, said linking group being a sterically hindered group.
  • the above linking group is preferably selected from the group consisting of a spirofluorenyl group, a phenyl group, a biphenyl group, a C 1-6 alkyl group or a phenyl group in which at least one substituted spiro group, a C 1-6 alkyl group or a phenyl group is used. a biphenyl group in which at least one substituted phenyl group or a C 1-6 alkyl group or a phenyl group is substituted with at least one of them.
  • the donor group is preferably selected from the following structures:
  • the acceptor group is preferably selected from the following structures:
  • the host material is selected from compounds having the following structure:
  • the anode may be an inorganic material or an organic conductive polymer.
  • the inorganic material is generally a metal oxide such as indium tin oxide (ITO), zinc oxide (ZnO) or indium zinc oxide (IZO) or a metal having a higher work function such as gold, copper or silver, preferably ITO;
  • the organic conductive polymer is preferably One of polythiophene/sodium polyvinylbenzenesulfonate (hereinafter referred to as PEDOT/PSS) and polyaniline (hereinafter referred to as PANI).
  • the cathode generally uses a metal having a lower work function such as lithium, magnesium, calcium, barium, aluminum or indium or an alloy thereof with copper, gold or silver, or an electrode layer in which metal and metal fluoride are alternately formed.
  • the cathode is preferably a laminated LiF layer and an Al layer (the LiF layer is on the outer side).
  • the material of the hole transport layer may be selected from the group consisting of aromatic amines and dendrite low molecular materials, preferably NPB.
  • the fluorescent dye is preferably a material such as a coumarin (e.g., DMQA, C545T) or a dipyran (e.g., DCJTB, DCM) compound.
  • a coumarin e.g., DMQA, C545T
  • a dipyran e.g., DCJTB, DCM
  • the material of the electron transport layer may be an organometallic complex (such as Alq 3 , Gaq 3 , BAlq or Ga (Saph-q)) or other materials commonly used for electron transport layers, such as aromatic fused rings (such as pentacene, hydrazine) or Phenanthroline (such as Bphen, BCP) compounds.
  • organometallic complex such as Alq 3 , Gaq 3 , BAlq or Ga (Saph-q)
  • other materials commonly used for electron transport layers such as aromatic fused rings (such as pentacene, hydrazine) or Phenanthroline (such as Bphen, BCP) compounds.
  • the organic electroluminescent device of the present invention may further have a hole injecting layer between the anode and the hole transporting layer, and the material of the hole injecting layer may be, for example, 4,4',4"-tris(3-methyl).
  • Phenylaniline)triphenylamine is doped with F4TCNQ, or copper phthalocyanine (CuPc), or may be a metal oxide such as molybdenum oxide or cerium oxide.
  • each of the above layers may be conventionally used in the thickness of these layers in the art.
  • the present invention also provides a method for preparing the organic electroluminescent device, as shown in FIG. 3, comprising sequentially depositing an anode 02, a hole transport layer 05, a light emitting layer 06, an electron transport layer 07, and a cathode stacked on each other on a substrate 01. 03, and then encapsulating, wherein the difference between the triplet state and the singlet state of the host material in the light-emitting layer 06 is less than 0.15 eV.
  • the substrate may be glass or a flexible substrate, and the flexible substrate may be a polyester-based, polyimide-based compound material or a thin metal sheet.
  • the lamination and encapsulation can take any suitable method known to those skilled in the art.
  • the luminous efficiency of the device was tested by a test device consisting of a keithley 2602 and a calibrated silicon photodiode.
  • the luminous efficiency is equal to the brightness measured by the test device divided by the current density.
  • the luminescence spectrum was tested by Pr655.
  • the luminescent layer comprises a host material (Host 1) and a fluorescent doping dye (YD 1), wherein the Host 1 material is the first type of host material, and the first three-line state of the (n- ⁇ ) excited state is slightly smaller than CT.
  • the first three-wire state (0.1 eV) of the excited state, the single-state energy level of the YD1 is 2.2 eV, which is lower than the single-line energy level of Host 1.
  • the structural formulas of Host 1 and YD 1 are as follows:
  • ITO 150 nm
  • NPB 40 nm
  • Host 1 (0.01%, 0.5%, 1.0%, 5%): YD 1 (30 nm) / Alq 3 (20 nm) / LiF (0.5 nm) / Al (150 nm)
  • the percentage in parentheses before YD1 indicates different fluorescent dye doping concentrations, and in the present embodiment and hereinafter, the doping concentration is % by weight.
  • the specific preparation method of the organic electroluminescent device is as follows:
  • the glass substrate is washed with detergent and deionized water, and placed under an infrared lamp to dry, and a layer of anode material is sputtered on the glass, the film thickness is 150 nm;
  • the above-mentioned glass substrate with an anode was placed in a vacuum chamber, evacuated to 1 ⁇ 10 -4 Pa, and NPB was continuously evaporated on the anode layer film as a hole transport layer at a film formation rate of 0.1 nm/ s, the vapor deposition film thickness was 40 nm.
  • the luminescent layer was evaporated on the hole transporting layer by a dual source co-evaporation method, and the mass percentage of Host 1 and YD 1 was controlled by a film thickness monitor to adjust the film formation rate.
  • the thickness of the deposited film was 30 nm.
  • a layer of Alq 3 material is continuously evaporated as an electron transport layer, the evaporation rate is 0.1 nm/s, and the total vapor deposition thickness is 20 nm;
  • a LiF layer and an Al layer are sequentially deposited on the above-mentioned light-emitting layer as a cathode layer of the device, wherein the LiF layer has an evaporation rate of 0.01 to 0.02 nm/s, a thickness of 0.5 nm, and an Al layer vapor deposition rate of 1.0. Nm/s, thickness 150 nm.
  • An organic electroluminescent device was prepared in the same manner as in the above Example 1, and the device was structured as follows:
  • ITO 150 nm
  • NPB 40 nm
  • ADN (0.01%, 0.5%, 1.0%, 5%)
  • YD 1 (30 nm) / Alq 3 (20 nm) / LiF (0.5 nm) / Al (150 nm)
  • the host material in the light-emitting layer of the device adopts ADN, which does not have a CT state transition.
  • the first three-line state using the (n- ⁇ ) excited state in the embodiment of the present invention is slightly smaller than the first three-wire state (0.1 eV) of the CT excited state.
  • the luminous efficiency of the light-emitting device prepared by the first type of host material is significantly higher than that of the light-emitting device using the host material in the absence of the CT state.
  • the doping concentration of the fluorescent dye is in the range of 0.5% to 1%, particularly high luminous efficiency can be obtained.
  • red light-emitting devices having different fluorescent dye doping concentrations were prepared, and these devices have a structure as shown in FIG.
  • the luminescent layer comprises a host material (Host2) and a fluorescent dopant dye (RD 1).
  • the triplet state of the CT excited state of Host2 and the (n- ⁇ ) excited state are very different (1.3eV) and the second triplet state of the (n- ⁇ ) excited state is higher than that of the CT excited state.
  • the RD1 single-line energy level is 2.0 eV
  • the RD1 single-line energy level is lower than the single-line energy level of Host 2.
  • the structure of Host 2 and RD1 are as follows:
  • An organic electroluminescent device was prepared in the same manner as in the above Example 1, the light-emitting device The structure is as follows:
  • ITO 150 nm
  • NPB 40 nm
  • Host 2 (0.01%, 0.5%, 1.0%, 5%, 10%): RD 1 (30 nm) / Bphen (20 nm) / LiF (0.5 nm) / Al (150 nm )
  • the percentage in parentheses before RD1 indicates different fluorescent dye doping concentrations.
  • An organic electroluminescent device was prepared in the same manner as in the above Example 1, and the structure of the light-emitting device was as follows:
  • Alq 3 is used as the host material of the light-emitting layer, and there is no CT state transition.
  • the triplet state of the CT excited state and the (n- ⁇ ) excited state of the embodiment of the present invention differ greatly (1.3 eV) and ( The second triplet state of the n- ⁇ ) excited state is higher than that of the first singlet state of the CT excited state, and the luminous efficiency is significantly higher than that of the conventional host material. Electroluminescent device. Further, when the doping concentration of the fluorescent dye is in the range of 0.01% to 1%, particularly high luminous efficiency can be obtained.
  • an organic electroluminescent device is prepared in the same manner as in the above-mentioned Embodiment 1, and the structure of the light-emitting device is as follows:
  • ITO 150 nm
  • NPB 40 nm
  • host material 0.5% YD 1 (30 nm) / Bphen (20 nm) / LiF (0.5 nm) / Al (150 nm).
  • OLED19 2-5 (0.5%) YD 1 (30 nm) 35 OLED20 2-6: (0.5%) YD 1 (30 nm) 12 OLED21 2-7: (0.5%) YD 1 (30 nm) 20.5 OLED22 2-8: (0.5%) YD 1 (30 nm) 33 OLED23 2-9: (0.5%) YD 1 (30 nm) 32 OLED24 2-10: (0.5%) YD 1 (30nm) 27 OLED25 2-11: (0.5%) YD 1 (30 nm) 25 OLED26 2-12: (0.5%) YD 1 (30nm) 36 OLED27 2-13: (0.5%) YD 1 (30 nm) 35 OLED28 2-14: (0.5%) YD 1 (30nm) 35 OLED29 2-15: (0.5%) YD 1 (30nm) 31 OLED30 3-1: (0.5%) YD 1 (30 nm) twenty three OLED31 3-2: (0.5%) YD 1 (30 nm) twenty one OLED32 3-3: (0.5%)

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Abstract

一种有机电致发光器件及其制造方法。有机电致发光器件的发光层（06）的主体材料为CT激发态的三线态能级高于n-π激发态的三线态能级，并且相差为0～0.3eV之间的材料；或者，发光层（06）的主体材料为CT激发态的三线态能级高于n-π激发态的三线态能级，其差值为1.0eV以上的材料，并且，主体材料的n-π激发态的第二三线态能级和CT激发态的第一单线态能级的差值为-0.1～0.1eV；发光染料为荧光染料。该有机电致发光器件能够充分利用发光层（06）中的三线态，实现荧光器件100%的发光效率，并无需使用贵金属从而减低成本。

Description

一种有机电致发光器件及其制备方法 技术领域
本发明属于有机电致发光器件领域，具体涉及一种有机电致发光器件及其制备方法。
背景技术
在电致激发的条件下，有机电致发光器件会产生25％的单线态和75％的三线态。传统的荧光材料由于自旋禁阻的原因只能利用25％的单线态激子，从而外量子效率仅仅限定在5％以内。几乎所有的三线态激子只能通过热的形式损失掉。为了提高有机电致发光器件的效率，必须充分利用三线态激子。
为了利用三线态激子，研究者提出了许多方法。最为显著的是磷光材料的利用。磷光材料由于引入了重原子，存在旋轨耦合效应，因此可以充分利用75％的三线态，从而实现100％的内量子效率。然而磷光材料由于使用了稀有的重金属，使得材料昂贵，不利于降低产品的成本。如果荧光器件能够很好的利用三线态激子则能很好地解决这个问题。研究者提出了在荧光器件中利用三线态淬灭产生单线态来提高荧光器件的效率，但是这种方法理论能达到的最大外量子效率仅仅有62.5％，远低于磷光材料。因此寻找新的技术充分利用荧光材料的三线态能级提高发光效率是非常必要的。
发明内容
为了解决上述技术问题，本发明提供了一种新的有机电致发光器件和其制备方法。
为了充分利用荧光器件中所产生的75％的三线态，提高器件的发光效率，降低器件成本，本发明提供了一种新的有机电致发光器件的发光层，该发光层中的主体材料为特定的存在电荷转移跃迁的材料。
本发明还提供了一种含有上述发光层的有机电致发光器件，其包括彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极。
本发明还提供所述有机电致发光器件的制备方法，包括在基板上依次沉积彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极，然后封装， 其中所述发光层中的主体材料发光层中的主体材料为特定的存在电荷转移跃迁的材料。
当一个主体材料中同时存在给体和受体基团时，往往会存在分子内的电荷转移跃迁(CT)，由此产生的激发态为CT态。同时材料由于杂原子的存在还会有诸如n-π跃迁等其他跃迁。因此，材料的单线态和三线态可以分为CT态单线态、(n-π)态跃迁单线态、CT态三线态以及(n-π)态跃迁三线态。CT激发态的能级往往高于(n-π)激发态。CT激发态的三线态会高于(n-π)激发态的三线态。二者的能级差可以具体用电子伏特来描述(eV)。根据材料结构的不同，可以分为三种情况，第一种为两者能级差很小，诸如0～0.3eV，另一种为两者相差很大，诸如1.0eV以上，第三种则是两者之差处于前两种之间。在这里，我们所选的主体材料为：CT激发态的三线态与(n-π)激发态的三线态能级差很小(0～0.3eV)的材料；或者，两者能级差很大(＞1.0eV)，但是(n-π)激发态的第二三线态要稍小或稍高于CT激发态的第一单线态的材料(二者相差0-0.1eV)。材料能级结构如图1和图2所示：
在第一类主体材料中，(n-π)激发态的第一三线态稍小于CT激发态的第一三线态(0～0.3eV)，因此在吸收外界热量的情况下会跃迁到能量高的CT激发态的第一三线态，又从第一三线态回到CT激发态的第一单线态，从而传递给染料发光。通过这一途径会充分利用主体材料的三线态。CT态可以在同时具有给体基团和受体基团的化合物中获得。由于空间上分离的给体和受体可以获得空间分离的HOMO与LUMO能级。CT态的三线态和单线态能极差与HOMO与LUMO的重叠成正比，因此分离的HOMO与LUMO能级可以获得小的CT态单线态和三线态的能极差，这种能级差一般小于0.3eV。这种材料的设计可以通过引入大体积的给体基团(如吲哚咔唑基)或者受体基团使得材料存在一定的扭曲从而获得空间的分离；或者通过引入具有空间扭曲的连接基团诸如螺芴基从而使得给体基团和受体基团分离。
在第二类主体材料中，(n-π)激发态的第一三线态远小于CT激发态的第一三线态能级(＞1.0eV)，因此在电致激发下，(n-π)激发态的第一三线态很少产生，主要产生(n-π)激发态的第二三线态，而第二三线态能量可以转移到CT激发态的第一单线态，从而也传递给染料发光，实现100％的发光效率。这种材料同时存在局域态和CT态，材料的局域态的单线态和三线态的能极差很大，使得单线态到三线态的系间窜越比较困难。同时，材料的CT态的三线态和局域态的单线态能级差很小，从而使得材料 的CT态三线态可以转移到单线态。要获得这种功能需要得到空间上有一定扭曲的材料，同时存在给体基团和受体基团从而获得CT态，同时，要求给体基团(或者受体基团)的局域单线态和三线态能极差比较大。根据文献报道，菲并咪唑基，萘并噻唑基、苯并噻唑基或者蒽基的单线态能级和三线态能级差在1.0eV以上，并且这种材料都为受体基团，因此结合一定的给体基团可以获得这种效果的化合物。
能级不适合这两类材料的其他主体材料，不能够有效地通过以上途径利用三线态，因此不予考虑。
本发明提供的有机电致发光器件，包括彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极，发光层包括主体材料和发光染料，其中，
发光层的主体材料为CT激发态的三线态能级高于n-π激发态的三线态能级，并且相差为0～0.3eV之间的材料；
或者，
发光层的主体材料为CT激发态的三线态能级高于n-π激发态的三线态能级，其差值为1.0eV以上的材料，并且，所述主体材料的n-π激发态的第二三线态能级和CT激发态的第一单线态能级的差值为-0.1～0.1eV；
发光染料为荧光染料。
优选地，所述荧光染料的单线态能级低于主体材料的单线态能级。
所述主体材料为存在电荷转移跃迁的材料，主体材料中同时存在给体基团单元和受体基团单元，
所述给体基团单元为一个给体基团或两个以上的给体基团连接构成的基团；
所述受体基团单元为一个受体基团或两个以上的受体基团连接构成的基团；
所述给体基团选自吲哚并咔唑基，咔唑基，联咔唑基，三苯胺基，吩噁嗪基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的吲哚并咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的联咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的三苯胺基，或者C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的吩噁嗪基；
所述受体基团选自萘基，蒽基，菲基，芘基，三嗪基，苯并咪唑基，氰基、吡啶基，砜基，菲并咪唑基，萘并噻唑基，苯并噻唑基，噁二唑基， C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的萘基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的蒽基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的菲基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的芘基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的三嗪基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的苯并咪唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的吡啶基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的砜基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的菲并咪唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的萘并噻唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的苯并噻唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的噁二唑基；
其中，一种或多种所述给体基团单元与一种或多种所述受体基团单元直接连接形成主体材料；或者，一种或多种所述给体基团单元和一种或多种所述受体基团单元分别与连接基团连接形成主体材料，所述连接基团为具有空间位阻的基团。
优选地，一种或两种给体基团单元和一种或两种受体基团单元分别与连接基团连接形成主体材料，或者一种或两种受体基团单元与一种或两种给体基团单元直接连接形成主体材料。
优选地，所述连接基团选自螺芴基、苯基、联苯基、C1-6的烷基或苯基的其中至少一种取代的螺芴基、C1-6的烷基或苯基的其中至少一种取代的苯基或者C1-6的烷基或苯基的其中至少一种取代的联苯基。
进一步优选地，所述给体基团选自以下基团
Figure PCTCN2014093904-appb-000001
Figure PCTCN2014093904-appb-000002
进一步优选地，所述受体基团选自以下基团：
Figure PCTCN2014093904-appb-000003
更优选地，所述主体材料具有以下结构：
Figure PCTCN2014093904-appb-000004
Figure PCTCN2014093904-appb-000005
Figure PCTCN2014093904-appb-000006
Figure PCTCN2014093904-appb-000007
Figure PCTCN2014093904-appb-000008
优选地，所述发光染料为三线态能级小于2.3eV的荧光染料。更优选的，荧光染料选自香豆素类或双吡喃类。
优选地，所述荧光染料在发光层中的掺杂浓度不高于5重量％。进一步优选地，所述荧光染料在发光层中的掺杂浓度为0.001重量％-1重量％。更优选地，所述荧光染料在发光层中的掺杂浓度为0.1重量％-1重量％。
优选地，空穴传输层的材料的三线态能级高于主体材料的三线态能级。进一步优选地，空穴传输层的材料的三线态能级高于2.5eV。更优选地，空 穴传输层的材料为芳胺类和/或枝聚物类低分子材料，最优选为N，N′-二苯基-N，N′-(1-萘基)-1，1′-联苯-4，4′-二胺。
优选地，电子传输层的材料的三线态能级高于2.5eV。
优选地，所述阳极和所述空穴传输层之间还设有空穴注入层。其中，空穴注入层的材料为4，4’，4”-三(3-甲基苯基苯胺)三苯胺掺杂F4TCNQ，或者铜酞菁，或为金属氧化物类，如氧化钼、氧化铼。
本发明提供上述的有机电致发光器件的制备方法，包括在基板上依次沉积彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极，然后封装。
本发明能够达到以下技术效果：
本发明中的有机电致发光器件由于利用了新的发光层主体材料，该主体材料含有给体基团和受体基团，能够充分利用发光层中产生的三线态，实现荧光器件中100％的发光效率，并且无需使用贵金属，降低了成本。
附图说明
图1：第一类材料有机电致发光器件发光层能量传输及发光示意图；
图2：第二类材料有机电致发光器件发光层能量传输及发光示意图；
图3：本发明的有机电致发光器件的基本结构示意图，
其中，01为基板，
02为阳极层，
03为阴极层，
04为空穴注入层，
05为空穴传输层，
06为发光层，
07为电子传输层。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好的理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
本发明的有机电致发光器件包括彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极，其中，发光层中的主体材料为CT激发态的三线态与(n-π)激发态的三线态能级相差很小(0～0.3eV)的材料以及两者相差很大(≥ 1.0eV)但是(n-π)激发态的第二三线态要稍小或稍高于CT激发态的第一单线态的材料(二者相差0～0.1eV)。本文中所选或者设计的材料在空间上都存在相互分离的给体基团和受体基团，从而导致了HOMO与LUMO能级的空间分离，减小了重叠积分，因此材料的CT态的单线态和三线态的能级差相差很小。同时，所选用的菲并咪唑基，萘并噻唑基、苯并噻唑基或者蒽基的单线态和三线态能级差在1.0eV以上，也可以达到第二类材料的要求。
优选将所述主体材料中掺杂荧光染料，并且所述荧光染料的单线态能级低于主体材料的CT态单线态能级。所选用的荧光染料的发光波长都比主体材料的发光波长要长，因此可以保证染料的单线态能级小于主体材料的单线态能级。通过掺杂荧光染料，主体材料的CT态单线态能级的能量可直接传递给荧光染料，能量转移使得CT态单线态激子的辐射寿命减小，从而有利于提高CT态三线态的利用效率，从而获得高的发光效率。
荧光染料浓度优选低于1％的质量浓度，优选荧光染料吸收光谱和主体发射光谱重叠较大的材料，有利于提高能量传递的效率，同时，减小短程的Dexter能量传递，因为这部分会损失掉激子。同时，本发明中的电子和空穴传输材料的三线态能级要高于主体材料的三线态能级，有利于限制发光层的激子。本发明中的荧光染料的三线态能级要小于2.3eV，而电子和空穴的三线态能级要高于2.5eV，因此可以有效限制发光层中的激子。
本发明有机电致发光器件的发光层包括主体材料和发光染料，该主体材料为存在电荷转移跃迁的材料，主体材料中同时存在给体基团单元和受体基团单元。其中，给体基团单元为一个给体基团或两个以上的给体基团连接构成的基团；受体基团单元为一个受体基团或两个以上的受体基团连接构成的基团；
具体的，主体材料的结构可为donor-connection-acceptor或者为donor-acceptor-donor的结构等。
给体基团选自吲哚并咔唑基，咔唑基，二连咔唑基，三苯胺基，吩噁嗪基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的吲哚并咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的二苯并呋喃基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的三苯胺基，或者C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的吩噁嗪基；
受体基团选自萘基，蒽基，菲基，芘基，三嗪基，苯并咪唑基，氰基、吡啶基，砜基，菲并咪唑基，萘并噻唑基，苯并噻唑基，噁二唑基，C1-6的 烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的萘基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的蒽基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的菲基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的芘基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的三嗪基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的苯并咪唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的吡啶基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的砜基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的菲并咪唑基；C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的萘并噻唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的苯并噻唑基或C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的噁二唑基；
其中，一种或多种所述给体基团单元与一种或多种所述受体基团单元直接连接形成主体材料；或者，一种或多种所述给体基团单元和一种或多种所述受体基团单元分别与连接基团连接形成主体材料，所述连接基团为具有空间位阻的基团。
上述连接基团优选选自螺芴基、苯基、联苯基、C1-6的烷基或苯基的其中至少一种取代的螺芴基、C1-6的烷基或苯基的其中至少一种取代的苯基或者C1-6的烷基或苯基的其中至少一种取代的联苯基。
给体基团优选选自以下结构：
Figure PCTCN2014093904-appb-000009
Figure PCTCN2014093904-appb-000010
受体基团优选选自以下结构：
Figure PCTCN2014093904-appb-000011
具体地，主体材料选自具有以下结构的化合物：
Figure PCTCN2014093904-appb-000012
1-1(Chem.Commun.，2012，48，9580-9582)
Figure PCTCN2014093904-appb-000013
1-2(Angew.Chem.Int.Ed.，2012，51，11311-11315)
Figure PCTCN2014093904-appb-000014
1-3(Chem.Commun.2012，48，11392-11394)
Figure PCTCN2014093904-appb-000015
1-4(J.Mater.Chem.C，2013，1，4599-4604)
Figure PCTCN2014093904-appb-000016
1-5(J.Mater.Chem.C，2013，1，4599-4604)
Figure PCTCN2014093904-appb-000017
1-6(Phys.Chem.Chem.Phys.，2013，15，15850)
Figure PCTCN2014093904-appb-000018
1-7(ΔEST＝0.11，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000019
1-8(ΔEST＝0.14，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000020
1-9(Nature，2012，492，234)
Figure PCTCN2014093904-appb-000021
1-10(Nature，2012，492，234)
Figure PCTCN2014093904-appb-000022
1-11(Nature，2012，492，234)
Figure PCTCN2014093904-appb-000023
1-12(ΔEST＝0.21，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000024
2-1(ΔEST＝0.15，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000025
2-2(ΔEST＝0.04，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000026
2-3
Figure PCTCN2014093904-appb-000027
2-4(J.AM.Chem.Soc.2012，134，14706-14709)
Figure PCTCN2014093904-appb-000028
2-5(J.AM.Chem.Soc.2012，134，14706-14709)
Figure PCTCN2014093904-appb-000029
2-6(Chem.Mater.，2013，25(18)，pp 3766-3771)
Figure PCTCN2014093904-appb-000030
2-7(ΔEST＝0.07，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000031
2-8(ΔEST＝0.16，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000032
2-9(ΔEST＝0.09，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000033
2-10(PRL，2013，110，247401)
Figure PCTCN2014093904-appb-000034
2-11(ΔEST＝0.06，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000035
2-12(Appl.Phys.Lett.，2012，101，093306)
Figure PCTCN2014093904-appb-000036
2-13(Phys.Chem.Chem.Phys.2013，15，15850)
Figure PCTCN2014093904-appb-000037
2-14((J.Mater.Chem.C，2013，1，4599-4604)
Figure PCTCN2014093904-appb-000038
2-15(J.Mater.Chem.C，2013，1，4599-4604)
Figure PCTCN2014093904-appb-000039
3-1(CC，DOI：10.1039/c3cc47130f)   3-2(CC，DOI：10.1039/c3cc47130f)
Figure PCTCN2014093904-appb-000040
3-3(CT态的ΔEST＝0.03，同时局域态单线态与三线态能极差在1.1eV，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000041
3-4(CT态的ΔEST＝0.05，同时局域态单线态与三线态能极差在1.2eV，利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000042
3-5(CT态的ΔEST＝0.01，同时局域态单线态与三线态能极差在1.4eV利用Gaussian 03/TD-DFT计算)
Figure PCTCN2014093904-appb-000043
3-6(AFM，DOI：10.1002/adfm.201301750)
本申请中相关化合物的合成：
1、化合物1-7的合成
Figure PCTCN2014093904-appb-000044
合成1-7a，
3.34g咔唑，3.22g 3，6-二溴咔唑，0.5g CuI，0.5g菲哕啉以及5.2g碳酸钾加入到100ml圆底烧瓶中，加入60mlDMF，在氮气氛围下加热回流反应48小时，随后将反应液倒入水中，减压抽滤得到固体。固体用色谱柱分离得到1-7a，产率为30％。
质谱数据：ESI-MS m/z：498[M+H]+，元素分析：C36H23N3：C：86.90，H：4.66，N：8.44。
合成1-7b，
3.11g三溴苯，2.48g对甲基苯硫酚，6g碳酸钾，1g碘化亚铜加入到100ml圆底烧瓶中，加入50ml的DMF，在氮气氛围下，100℃加热24小时。随后将反应液倒入水中，减压抽滤得到固体。固体用色谱柱分离得到1-7b，产率为60％。
质谱数据：ESI-MS m/z：401[M+H]+，元素分析：C20H17BrS，C：59.85，H：4.27。
合成1-7c，
在冰水浴下，将溶于30ml的1-7b缓慢滴加到1g mCPBA的二氯甲烷溶液中，保持在冰水浴中加完，随后反应12h。固体用色谱柱分离得到1-7c，产率为99％。
质谱数据：ESI-MS m/z：465[M+H]+，元素分析：C20H17BrO4S2，C：86.90，H：4.66，N：8.44。
合成1-7，
4.97g 1-7a，4.63g 1-7b，0.5g CuI，0.5g菲哕啉以及5.2g碳酸钾加入到100ml圆底烧瓶中，加入60ml DMF，在氮气氛围下加热回流反应48小时，随后将反应液倒入水中，减压抽滤得到固体。固体用色谱柱分离得到1-7，产率为60％。
质谱数据：ESI-MS m/z：882[M+H]+，元素分析：C56H39N3O4S2，C 76.25，H 4.46，N 4.76.
2、化合物1-4的合成
1-4的合成参照1-7，物质检测数据：质谱数据：ESI-MS m/z：717[M+H]+，元素分析C44H32N2O4S2，C：73.72，H：4.50，N：3.91。
3、化合物1-8的合成
Figure PCTCN2014093904-appb-000045
4.52g 1-8a，3g 1-8b和0.05g四三苯基膦钯催化剂，以及5.4g碳酸钾，加入到圆底烧瓶中，再加入30ml甲苯和20ml水以及5ml乙醇，在85℃下反应48h。反应结束用二氯甲烷萃取，得到有机层，然后用色谱柱分离，得到1-8，产率为65％。
质谱数据：ESI-MS m/z：640[M+H]+，元素分析：C45H29N5，C：84.48，H：4.57，N：10.95。
4、化合物2-1的合成
Figure PCTCN2014093904-appb-000046
2.43g 2-1a加入到0.24g NaH的超干DMF溶液中(30ml)，室温搅拌30min，然后将2.54g 2-1b的DMF溶液滴加到上述溶液中，加热100度搅拌1小时，冷却后倒入水中，过滤固体，用色谱柱分离。得到2-1。
质谱数据：ESI-MS m/z：701[M+H]+，元素分析：C48H32N2O2S，C：82.26，H：4.60，N：4.0。
5、化合物2-2的合成
化合物2-2的合成参见2-1，方法与化合物2-1基本相同，区别在于将2-1a换成二联咔唑。
质谱数据：ESI-MS m/z：879[M+H]+，元素分析：C60H38N4O2S，C：81.98，H：4.36，N：6.37。
6、化合物2-7的合成
Figure PCTCN2014093904-appb-000047
合成2-7a，
2.25g 2，4-二氯-6-苯三嗪，2g间溴苯硼酸，0.05g四三苯基膦钯催化剂，以及5.4g碳酸钾，加入到圆底烧瓶中，再加入30ml甲苯和20ml水以及5ml乙醇，在85℃下反应48h。反应结束用二氯甲烷萃取，得到有机层，然后用色谱柱分离，得到2-7a，产率为58％。
质谱数据：ESI-MS m/z：466[M+H]+，元素分析：C21H13Br2N3，C：53.99，H：2.80，N：8.99。
合成2-7，
4.65g 2-7a，3.66g吩噁嗪，0.5g CuI，0.5g菲哕啉以及5.2g碳酸钾加入到100ml圆底烧瓶中，加入60ml DMF，在氮气氛围下加热回流反应48小时，随后将反应液倒入水中，减压抽滤得到固体，固体用色谱柱分离得到2-7，产率为48％。
质谱数据：ESI-MS m/z：672[M+H]+.元素分析：C45H29N5O2，C：80.46，H：4.35，N：4.76。
7、化合物2-8的合成
合成2-8a，
2.25g 2，4-二氯-6-苯三嗪，2g对溴苯硼酸，0.05g四三苯基膦钯催化剂，以及5.4g碳酸钾，加入到圆底烧瓶中，再加入30ml甲苯和20ml水以及5ml乙醇，在85℃下反应48h。反应结束用二氯甲烷萃取，得到有机层，然后用色谱柱分离，得到2-8a，产率为55％。
质谱数据：ESI-MS m/z：466[M+H]+，元素分析：C21H13Br2N3，C：53.99，H：2.80，N：8.99。
合成2-8，
4.65g 2-8a，3.66g吩噁嗪，0.5g CuI，0.5g菲哕啉以及5.2g碳酸钾加入到100ml圆底烧瓶中，加入60ml DMF，在氮气氛围下加热回流反应48小时，随 后将反应液倒入水中，减压抽滤得到固体，固体用色谱柱分离得到2-8，产率为56％。
质谱数据：ESI-MS m/z：640[M+H]+，元素分析：C45H29N5，C：84.48，H：4.57，N：10.95。
8、化合物2-9的合成
2-9的合成参见2-7，区别在于换用不同的给体基团.，选用的咔唑替换吩噁嗪。4.65g 2-8a，3.0g咔唑，0.5g CuI，0.5g菲哕啉以及5.2g碳酸钾加入到100ml圆底烧瓶中，加入60ml DMF，在氮气氛围下加热回流反应48小时，随后将反应液倒入水中，减压抽滤得到固体，固体用色谱柱分离得到2-9，产率为50％。
质谱数据：ESI-MS m/z：640[M+H]+，元素分析：C45H29N5，C：84.48，H：4.57，N：10.95。
9、化合物2-11的合成
Figure PCTCN2014093904-appb-000048
合成2-11，
3.32g苯基吲哚咔唑，2.67g 2-氯-4，6-二苯三嗪，0.5g CuI，0.5g菲哕啉以及5.2g碳酸钾加入到100ml圆底烧瓶中，加入60ml DMF，在氮气氛围下加热回流反应48小时，随后将反应液倒入水中，减压抽滤得到固体。固体用色谱柱分离得到2-7，产率为48％。
质谱数据：ESI-MS m/z：564[M+H]+，元素分析：C39H25N5，C：83.10，H：4.47，N：12.43。
10、化合物3-3的合成
Figure PCTCN2014093904-appb-000049
合成3-3a，
3ml吡啶加入到邻苯二胺(0.6g)和氯化亚砜(5ml)的混合溶液中，在60度温度下搅拌10小时，用二氯甲烷萃取，然后用大量的水清洗，得到固体。
质谱数据：ESI-MS m/z：205。
合成3-3b，
2.25g 3-3a，2g苯硼酸，0.05g四三苯基膦钯催化剂，以及5.4g碳酸钾，加入到圆底烧瓶中，再加入30ml甲苯和20ml水以及5ml乙醇，在85℃下反应48h。反应结束用二氯甲烷萃取，得到有机层，然后用色谱柱分离，得到3-3a，产率为58％。
质谱数据：ESI-MS m/z：246[M+H]+。
合成3-3，
2.46g 3-3b，2.39g 4-硼酸三苯胺，0.05g四三苯基膦钯催化剂，以及5.4g碳酸钾，加入到圆底烧瓶中，再加入30ml甲苯和20ml水以及5ml乙醇，在85℃下反应48h，反应结束用二氯甲烷萃取，得到有机层，然后用色谱柱分离，得到3-3，产率为58％。
质谱数据：ESI-MS m/z：456[M+H]+，元素分析：C30H21N3S，C：79.09，H：4.65，N：9.22。
11、化合物3-4的合成
化合物3-4的合成参见化合物3-3，步骤基本相同，区别在于受体基团采用的是噻吩取代的苯并噻唑。
质谱数据：ESI-MS m/z：462[M+H]+，元素分析：C28H19N3S2：C：72.86，H：4.15，N：9.10。
12、化合物3-5的合成
化合物3-5的合成参见化合物3-3，步骤基本相同，区别在于：受体基团采用的是噻吩取代的萘并噻唑。
质谱数据：ESI-MS m/z：512[M+H]+，元素分析：C32H21N3S2：C：75.12，H：4.15，N：8.21。
本发明的有机发光显示器件实施例：阳极可以采用无机材料或有机导电聚合物。无机材料一般为氧化铟锡(ITO)、氧化锌(ZnO)、氧化铟锌(IZO)等金属氧化物或金、铜、银等功函数较高的金属，优选ITO；有机导电聚合物优选为聚噻吩/聚乙烯基苯磺酸钠(以下简称PEDOT/PSS)、聚苯胺(以下简称PANI)中的一种。
阴极一般采用锂、镁、钙、锶、铝、铟等功函数较低的金属或它们与铜、金、银的合金，或金属与金属氟化物交替形成的电极层。本发明中阴极优选为层叠的LiF层和Al层(LiF层在外侧)。
空穴传输层的材料可以选自芳胺类和枝聚物类低分子材料，优选NPB。
荧光染料优选为香豆素类(如DMQA、C545T)或双吡喃类(如DCJTB、DCM)化合物等材料。
电子传输层的材料可采用有机金属配合物(如Alq3、Gaq3、BAlq或Ga(Saph-q))或其他常用于电子传输层的材料，如芳香稠环类(如pentacene、苝)或邻菲咯啉类(如Bphen、BCP)化合物。
本发明的有机电致发光器件还可在阳极和空穴传输层之间具有空穴注入层，所述空穴注入层的材料例如可采用4，4′，4″-三(3-甲基苯基苯胺)三苯胺掺杂F4TCNQ，或者采用铜酞菁(CuPc)，或可为金属氧化物类，如氧化钼，氧化铼。
上述各层的厚度可采用本领域中这些层常规的厚度。
本发明还提供所述有机电致发光器件的制备方法，如图3所示，包括在基板01上依次沉积彼此层叠的阳极02、空穴传输层05、发光层06、电子传输层07及阴极03，然后封装，其中所述发光层06中的主体材料的三线态与单线态能级差小于0.15eV。
所述基板可以是玻璃或是柔性基片，所述柔性基片可采用聚酯类、聚酰亚胺类化合物材料或者薄金属片。所述层叠及封装可采用本领域技术人员已知的任意合适方法。
下文通过实施例进一步说明本发明。
为方便起见，把本说明书中涉及的一些有机材料的缩写及全称列示如下：
Figure PCTCN2014093904-appb-000050
Figure PCTCN2014093904-appb-000051
Figure PCTCN2014093904-appb-000052
Figure PCTCN2014093904-appb-000053
Figure PCTCN2014093904-appb-000054
以下实施例中，器件的发光效率通过keithley2602与校准后的硅光二极管组成的测试装置进行测试。发光效率等于该测试装置测得的亮度除以电流密度。发光光谱通过Pr655测试。
实施例1
本实施例中制备了具有不同荧光染料掺杂浓度的黄色发光器件，这些器件具有如图3所示的结构。发光层包含一种主体材料(Host 1)及一种荧光掺杂染料(YD 1)，其中Host 1材料为第一类主体材料，其(n-π)激发态的第一三线态稍小于CT激发态的第一三线态(0.1eV)，YD1单线态能级为2.2eV，低于Host 1的单线态能级。Host 1与YD 1的结构式分别如下：
Figure PCTCN2014093904-appb-000055
本实施例的器件结构如下：
ITO(150nm)/NPB(40nm)/Host 1：(0.01％、0.5％、1.0％、5％)：YD 1(30nm)/Alq3(20nm)/LiF(0.5nm)/Al(150nm)
其中，YD1之前的括号中的百分比表示不同的荧光染料掺杂浓度，在本实施例以及下文中，掺杂浓度均为重量％。
所述有机电致发光器件的具体制备方法如下：
首先，利用洗涤剂和去离子水对玻璃基片进行清洗，并放置在红外灯下烘干，在玻璃上溅射一层阳极材料，膜厚为150nm；
然后，把上述带有阳极的玻璃基片置于真空腔内，抽真空至1×10-4 Pa，在上述阳极层膜上继续蒸镀NPB作为空穴传输层，成膜速率为0.1nm/s，蒸镀膜厚为40nm。
在空穴传输层上蒸镀发光层，采用双源共蒸的方法进行，Host 1与YD 1的质量百分比通过膜厚监控仪，调整成膜速率进行控制。蒸镀膜厚为30nm。
在发光层之上，继续蒸镀一层Alq3材料作为电子传输层，其蒸镀速率为0.1nm/s，蒸镀总膜厚为20nm；
最后，在上述发光层之上依次蒸镀LiF层和Al层作为器件的阴极层，其中LiF层的蒸镀速率为0.01～0.02nm/s，厚度为0.5nm，Al层的蒸镀速率为1.0nm/s，厚度为150nm。
对比例1
以与上述实施例1相同的方法制备有机电致发光器件，该器件结构如下：
ITO(150nm)/NPB(40nm)/ADN：(0.01％、0.5％、1.0％、5％)YD 1(30nm)/Alq3(20nm)/LiF(0.5nm)/Al(150nm)
即该器件的发光层中的主体材料采用ADN，其不具备CT态跃迁。
Figure PCTCN2014093904-appb-000056
将上面实施例1和对比例1的有机电致发光器件的性能表示在下表1中：
表1
Figure PCTCN2014093904-appb-000057
Figure PCTCN2014093904-appb-000058
由表1可以看出，在相同的荧光染料掺杂浓度下，本发明实施例中采用(n-π)激发态的第一三线态稍小于CT激发态的第一三线态(0.1eV)的第一类主体材料所制备的发光器件的发光效率明显高于使用不存在CT态的主体材料的发光器件。
并且，在荧光染料的掺杂浓度在0.5％-1％的范围时，尤其可获得高发光效率。
实施例2
本实施例中制备了具有不同荧光染料掺杂浓度的红色发光器件，这些器件具有如图3所示的结构。发光层包含一种主体材料(Host2)及一种荧光掺杂染料(RD 1)。其中Host2的CT激发态的三线态与(n-π)激发态的三线态能级差很大(1.3eV)且(n-π)激发态的第二三线态要高于其CT激发态的第一单线态，RD1单线态能级为2.0eV，并且RD1单线态能级低于Host 2的单线态能级。Host 2和RD1结构式分别如下：
Figure PCTCN2014093904-appb-000059
以与上述实施例1相同的方法制备有机电致发光器件，该发光器件的 结构如下：
ITO(150nm)/NPB(40nm)/Host 2：(0.01％、0.5％、1.0％、5％、10％)：RD 1(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
其中，RD1之前的括号中的百分比表示不同的荧光染料掺杂浓度。
对比例2
以与上述实施例1相同的方法制备有机电致发光器件，该发光器件的结构如下：
ITO(150nm)/NPB(40nm)/Alq3：(0.01％、0.5％、1.0％、5％、10％)RD 1(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
即采用Alq3作为发光层主体材料，其不存在CT态跃迁。
实施例和对比例2的有机电致发光器件的性能如下表2所示：
表2
Figure PCTCN2014093904-appb-000060
由表2可以看出，在相同的荧光染料掺杂浓度下，本发明实施例中采用CT激发态的三线态与(n-π)激发态的三线态能量相差很大(1.3eV)且(n-π)激发态的第二三线态要高于其CT激发态的第一单线态的主体材料所制备的发光器件，发光效率明显高于使用常规主体材料的有 机电致发光器件。且荧光染料的掺杂浓度在0.01％-1％的范围时，尤其可获得高发光效率。
实施例3
为测试本发明的主体材料对有机电致发光器件性能的影响，本实施例以与上述实施例1相同的方法制备有机电致发光器件，该发光器件的结构如下：
ITO(150nm)/NPB(40nm)/主体材料：0.5％YD 1(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)。
有机电致发光器件的性能表示在下表3中：
表3
  发光层结构 电流效率cd/A
OLED3 1-1：(0.5％)YD 1(30nm) 20
OLED4 1-2：(0.5％)YD 1(30nm) 24
OLED5 1-3：(0.5％)YD 1(30nm) 30
OLED6 1-4：(0.5％)YD 1(30nm) 24
OLED7 1-5：(0.5％)YD 1(30nm) 34
OLED8 1-6：(0.5％)YD 1(30nm) 36
OLED9 1-7：(0.5％)YD 1(30nm) 28
OLED10 1-8：(0.5％)YD 1(30nm) 31
OLED11 1-9：(0.5％)YD 1(30nm) 29
OLED12 1-10：(0.5％)YD 1(30nm) 19
OLED13 1-11：(0.5％)YD 1(30nm) 17
OLED14 1-12：(0.5％)YD 1(30nm) 23
OLED15 2-1：(0.5％)YD 1(30nm) 19
OLED16 2-2：(0.5％)YD 1(30nm) 36
OLED17 2-3：(0.5％)YD 1(30nm) 28
OLED18 2-4：(0.5％)YD 1(30nm) 24
OLED19 2-5：(0.5％)YD 1(30nm) 35
OLED20 2-6：(0.5％)YD 1(30nm) 12
OLED21 2-7：(0.5％)YD 1(30nm) 20.5
OLED22 2-8：(0.5％)YD 1(30nm) 33
OLED23 2-9：(0.5％)YD 1(30nm) 32
OLED24 2-10：(0.5％)YD 1(30nm) 27
OLED25 2-11：(0.5％)YD 1(30nm) 25
OLED26 2-12：(0.5％)YD 1(30nm) 36
OLED27 2-13：(0.5％)YD 1(30nm) 35
OLED28 2-14：(0.5％)YD 1(30nm) 35
OLED29 2-15：(0.5％)YD 1(30nm) 31
OLED30 3-1：(0.5％)YD 1(30nm) 23
OLED31 3-2：(0.5％)YD 1(30nm) 21
OLED32 3-3：(0.5％)YD 1(30nm) 25
OLED33 3-4：(0.5％)YD 1(30nm) 16
OLED34 3-5：(0.5％)YD 1(30nm) 14
OLED35 3-6：(0.5％)YD 1(30nm) 11
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (18)

  1. 一种有机电致发光器件，包括彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极，发光层包括主体材料和发光染料，其特征在于：
    发光层的主体材料为CT激发态的三线态能级高于n-π激发态的三线态能级，并且相差为0～0.3eV之间的材料；
    或者，
    发光层的主体材料为CT激发态的三线态能级高于n-π激发态的三线态能级，其差值为1.0eV以上的材料，并且，所述主体材料的n-π激发态的第二三线态能级和CT激发态的第一单线态能级的差值为-0.1～0.1eV；
    发光染料为荧光染料。
  2. 根据权利要求1所述的有机电致发光器件，其特征在于，所述发光层的主体材料的单线态和三线态能级差为0～0.3eV。
  3. 根据权利要求1所述的有机电致发光器件，其特征在于，所述荧光染料的单线态能级低于主体材料的单线态能级。
  4. 根据权利要求1所述的有机电致发光器件，其特征在于，所述主体材料为存在电荷转移跃迁的材料，主体材料中同时存在给体基团单元和受体基团单元，
    所述给体基团单元为一个给体基团或两个以上的给体基团连接构成的基团；
    所述受体基团单元为一个受体基团或两个以上的受体基团连接构成的基团；
    所述给体基团选自吲哚并咔唑基，咔唑基，联咔唑基，三苯胺基，吩噁嗪基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的吲哚并咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的联咔唑基，C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的三苯胺基，或者C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的吩噁嗪基；
    所述受体基团选自萘基，蒽基，菲基，芘基，三嗪基，苯并咪唑基，氰基、吡啶基，砜基，菲并咪唑基，萘并噻唑基，苯并噻唑基，噁二唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的萘基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的蒽基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的菲基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的芘基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的三嗪 基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的苯并咪唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的吡啶基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的砜基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的菲并咪唑基；C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的萘并噻唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的苯并噻唑基，C1-6的烷基、甲氧基、乙氧基、苯基或吡啶基中一种以上的基团取代的噁二唑基；
    其中，一种或多种所述给体基团单元与一种或多种所述受体基团单元直接连接形成主体材料；或者，一种或多种所述给体基团单元和一种或多种所述受体基团单元分别与连接基团连接形成主体材料，所述连接基团为具有空间位阻的基团。
  5. 根据权利要求4所述的有机电致发光器件，其特征在于，一种或两种给体基团单元和一种或两种受体基团单元分别与连接基团连接形成主体材料，或者一种或两种受体基团单元与一种或两种给体基团单元直接连接形成主体材料。
  6. 根据权利要求4所述的有机电致发光器件，其特征在于，所述连接基团选自螺芴基、苯基、联苯基、C1-6的烷基或苯基的其中至少一种取代的螺芴基、C1-6的烷基或苯基的其中至少一种取代的苯基或者C1-6的烷基或苯基的其中至少一种取代的联苯基。
  7. 根据权利要求4所述的有机电致发光器件，其特征在于，所述给体基团选自以下基团：
    Figure PCTCN2014093904-appb-100001
    Figure PCTCN2014093904-appb-100002
  8. 根据权利要求4所述的有机电致发光器件的发光层，其特征在于，所述受体基团选自以下基团：
    Figure PCTCN2014093904-appb-100003
  9. 根据权利要求4所述的有机电致发光器件，其特征在于，所述主体材料具有以下结构：
    Figure PCTCN2014093904-appb-100004
    Figure PCTCN2014093904-appb-100005
    Figure PCTCN2014093904-appb-100006
    Figure PCTCN2014093904-appb-100008
  10. 根据权利要求1所述的有机电致发光器件，其特征在于，所述发光染料为三线态能级小于2.3eV的荧光染料。
  11. 根据权利要求10所述的有机电致发光器件，其特征在于，所述荧光染料在发光层中的掺杂浓度不高于5重量％。
  12. 根据权利要求11所述的有机电致发光器件，其特征在于，所述荧光染料在发光层中的掺杂浓度为0.001重量％-1重量％。
  13. 根据权利要求11所述的有机电致发光器件，其特征在于，所述荧光染料在发光层中的掺杂浓度为0.1重量％-1重量％。
  14. 根据权利要求1所述的有机电致发光器件，其特征在于，空穴传输层的材料的三线态能级高于主体材料的三线态能级。
  15. 根据权利要求14所述的有机电致发光器件，其特征在于，空穴传输层的材料的三线态能级高于2.5eV。
  16. 根据权利要求1所述的有机电致发光器件，其特征在于，电子传输层的材料的三线态能级高于2.5eV。
  17. 根据权利要求1所述的有机电致发光器件，其特征在于，所述阳极和所述空穴传输层之间还设有空穴注入层。
  18. 权利要求1所述的有机电致发光器件的制备方法，包括在基板上依次沉积彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极，然后封装。
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