WO2018006680A1 - 高Tg有机电子传输材料 - Google Patents
高Tg有机电子传输材料 Download PDFInfo
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- WO2018006680A1 WO2018006680A1 PCT/CN2017/087506 CN2017087506W WO2018006680A1 WO 2018006680 A1 WO2018006680 A1 WO 2018006680A1 CN 2017087506 W CN2017087506 W CN 2017087506W WO 2018006680 A1 WO2018006680 A1 WO 2018006680A1
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- spirobifluorene
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- electron transporting
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 claims abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 4
- -1 diphenylphenyl group Chemical group 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- ZTISECWDPWDTAH-UHFFFAOYSA-N 1-bromo-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=C2C(Br)=CC=C1 ZTISECWDPWDTAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002274 desiccant Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- GPRIERYVMZVKTC-UHFFFAOYSA-N p-quaterphenyl Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 GPRIERYVMZVKTC-UHFFFAOYSA-N 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000005023 xylyl group Chemical group 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 5
- 239000011368 organic material Substances 0.000 abstract description 4
- 230000000877 morphologic effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 43
- 230000000903 blocking effect Effects 0.000 description 9
- 230000005684 electric field Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229940125782 compound 2 Drugs 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 5
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001894 space-charge-limited current method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 0 *c1c(ccc2c3nccc2I)c3ncc1 Chemical compound *c1c(ccc2c3nccc2I)c3ncc1 0.000 description 1
- ONCCVJKFWKAZAE-UHFFFAOYSA-N 2-bromo-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=C(Br)C=C12 ONCCVJKFWKAZAE-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Definitions
- the invention relates to a novel high Tg organic electron transport material, belonging to the field of electroluminescent materials.
- Electron-only organic semiconductor diode devices are one type of single-carrier devices that are used as power semiconductor devices for switches or rectifiers of smart digital power integrated circuits.
- the electron transporting material of the present invention can also be applied to an organic electroluminescent device and a field effect transistor.
- Electron-only organic semiconductor diode devices are devices prepared by spin coating or depositing one or more layers of organic materials between electrodes of two metals, inorganic or organic compounds.
- a classic layer of electronically only organic semiconductor diode device comprises an anode, an electron transport layer and a cathode.
- a hole blocking layer may be added between the anode and the electron transporting layer of the multilayer electronic-only semiconductor diode device, and an electron injecting layer may be added between the electron transporting layer and the cathode.
- the hole blocking layer, the electron transport layer and the electron injecting layer are respectively composed of a hole blocking material, an electron transporting material, and an electron injecting material.
- BPhen bathophenanthroline
- BCP bathocuproine
- the present invention provides an organic electron transporting material which can be applied to a high-life stability in a long-life electron-only semiconductor diode device and an organic electroluminescent device.
- the 9,9'-spirobifluorene linkage position is 1-, 2-, 3-, or 4-position; wherein, Ar 1 and Ar 2 are independently represented as unsubstituted or C1-C6 substituted C6-C25 aromatic base.
- Ar 1 , Ar 2 are independently represented by a C1-C5 alkyl group or a phenyl substituted or unsubstituted phenyl, naphthyl, anthryl, phenanthryl, anthracenyl, fluorenyl, fluoranthenyl, (9, 9-Dialkyl substituted or unsubstituted aryl) fluorenyl or 9,9-spiropurinyl.
- the 9,9'-spirobifluorene linkage position is 2- or 4-position; wherein Ar 1 and Ar 2 are independently represented by phenyl, tolyl, xylyl, naphthyl, methylnaphthalene, Biphenyl, diphenylphenyl, naphthylphenyl, diphenylbiphenyl, (9,9-dialkyl)indenyl, (9,9-dimethyl substituted or unsubstituted phenyl) anthracene Base, 9, 9-threaded base.
- Ar 1 and Ar 2 are independently represented by phenyl, tolyl, xylyl, naphthyl, methylnaphthalene, Biphenyl, diphenylphenyl, naphthylphenyl, diphenylbiphenyl, (9,9-dialkyl)indenyl, (9,9-dimethyl substituted or unsubstituted phenyl) anthracene Base
- Ar 1 and Ar 2 are represented by a phenyl group.
- the 9,9'-spirobifluorene linkage position is 2- or 4-position;
- the compound of formula (I) is the following structural compound:
- the preparation method of the high Tg organic electron transporting material comprises the following steps:
- the reaction condition of the step (1) is as follows: a solution of n-butyllithium in n-hexane (42 mL, 1.25 M) is slowly added dropwise to a solution of bromo 9,9'-spirobifluorene in anhydrous tetrahydrofuran. Temperature -90--80 °C.
- the reaction condition of the 9,9'-spirobifluorene of the step (2) and the formula (II) is: adding the dissolved formula (II) to the reaction mixture of the step (1) at -90--80 ° C Anhydrous tetrahydrofuran solution, stirred at room temperature after the dropwise addition, 6-10 hours.
- the extraction and purification of the target product are further included.
- the extraction and purification methods are: evaporating the solvent to the reaction mixture, adding water and acetic acid, combining the organic layers, drying with a desiccant, and spinning the solvent in the organic layer. Dry, acetone beaten, suction filtration, and the filtrate is the target product of purification.
- the material of the present invention can be used in an electron-only semiconductor diode device comprising an anode, a cathode, and an organic layer, the anode and cathode being a metal, an inorganic or an organic compound; the organic layer being a hole blocking layer, an electron transport layer, and an electron One or more layers in the injection layer; the electron transport layer being composed of an electron transport material having a compound of the formula (I). It is particularly noted that the above organic layers may be present in each of the layers as needed.
- the hole transport layer, the electron transport layer and/or the electron injection layer contains the compound of the formula (I), and the compound of the formula (I) is a hole blocking material, an electron transport material, and an electron. Inject material.
- the organic layer has a total thickness of from 1 to 1000 nm, preferably from 1 to 500 nm, more preferably from 5 to 300 nm.
- the organic layer is one or more layers of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. It is particularly noted that the above organic layers may be present in each of the layers as needed.
- the hole transport layer, the electron transport layer and/or the light-emitting layer contain the compound of the formula (I).
- the organic layer may be formed into a film by steaming or spin coating.
- the material of the invention can also be used in organic electroluminescent devices wherein the organic layer has a total thickness of from 1 to 1000 nm, preferably from 1 to 500 nm, more preferably from 50 to 300 nm.
- the organic electroluminescent device of the present invention comprises one or more light-emitting layers containing the compound of the formula (I) of the present invention.
- the luminescent layer is a host-guest doping system or a single luminescent material system composed of a host material and a guest material.
- the material experiments show that the compound of the formula (I) of the present invention has a high glass transition temperature, thus demonstrating that the compound of the formula (I) of the present invention has an organic material having high form stability.
- the device experiments show that only the electronic organic semiconductor diode device and the organic electroluminescent device prepared by using the organic electron transporting material of the present invention have good and stable performance and long device life.
- Figure 1 is a structural view of a device of the present invention
- 10 represents a glass substrate
- 20 represents an anode
- 30 represents a hole blocking layer
- 40 represents an electron transport layer
- 50 represents an electron injecting layer
- 60 represents a cathode.
- Figure 3 is a 13 C NMR chart of Compound 2.
- Figure 5 is a TGA diagram of Compound 2.
- Figure 6 is a DSC chart of Compound 2.
- Example 7 is a graph showing relationship between current density and electric field strength of Example 2, Example 3, and Example 4,
- Fig. 8 is a graph showing the relationship between the current density and the electric field intensity of Comparative Example 1 and Comparative Example 2.
- An electron-only organic semiconductor diode device was prepared using the compound of Example 1 of the present invention as an organic electron transporting material, as shown in FIG.
- the transparent conductive ITO glass substrate 10 (with the anode 20 on the surface) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
- a compound 2 having a thickness of 100 nm was vapor-deposited on the hole blocking layer as the electron transport layer 40.
- lithium fluoride of 1 nm thick was vapor-deposited on the electron transport layer as the electron injection layer 50.
- SCLC space charge limited current
- J is the current density (mA cm -2 )
- ⁇ is the relative dielectric constant (the organic material usually takes 3)
- ⁇ 0 is the vacuum dielectric constant (8.85 ⁇ 10 -14 C V -1 cm -1 )
- E is the electric field strength (V cm -1 )
- L is the thickness (cm) of the sample in the device
- ⁇ 0 is the charge mobility under the electric field (cm 2 V -1 s -1 )
- ⁇ is the Poole–Frenkel factor. Indicates how quickly the mobility changes with the strength of the electric field.
- the device produced in E electron mobility under operating electric field is 1x 10 6 Vcm -1 was 4.25x 10 -4 cm 2 V -1 s -1.
- the method was the same as in Example 2 except that a commonly used commercially available compound TmPyPB was used as the electron transport layer 40, and an electron-only semiconductor diode device for comparison was fabricated.
- the device produced in E electron mobility under operating electric field is 1x 10 6 Vcm -1 was 1.34x 10 -5 cm 2 V -1 s -1.
- Comparing the data of devices 1-3 and 4-5 shows that material compound 2 has a 30-fold higher electron mobility than the conventional TmPyPB under the same working electric field, and the glass transition temperature is three times higher due to device lifetime and material vitrification.
- the transition temperature the higher the glass transition temperature of the material, the better the device stability and the longer the life, so the material of the present invention is applicable to a long-life electronic-only semiconductor diode device and an organic electroluminescent device. Morphologically stable organic electron transport material.
Abstract
提供具有式(I)所述的化合物，其中，9，9'-螺二芴连接的位置为1-,2-,3-或4-位，Ar 1、Ar 2独立地表示为未取代或者C1-C6取代的C6-C25芳基。式(I)所述的化合物具有高玻璃化转变温度，为高形态稳定性的有机材料。使用该有机电子传输材料制备的仅电子有机半导体二极管器件及有机致电发光器件性能良好、稳定和寿命长。
Description
本发明涉及新型的高Tg有机电子传输材料，属于电子发光材料领域。
仅电子有机半导体二极管器件是单载流子器件的一种，作为功率半导体装置用于智能数字功率集成电路的开关或整流器。其中本发明的电子传输材料也可应用于有机电致发光器件及场效应晶体管。
仅电子有机半导体二极管器件为在两个金属、无机物或有机化合物的电极之间通过旋涂或沉积一层或多层有机材料而制备的器件。一个经典的一层仅电子有机半导体二极管器件包含阳极，电子传输层和阴极。在多层仅电子有机半导体二极管器件阳极和电子传输层之间可以加入空穴阻挡层，而电子传输层和阴极之间可以加入电子注入层。空穴阻挡层，电子传输层和电子注入层分别由空穴阻挡材料，电子传输材料和电子注入材料组成。连接到仅电子有机半导体二极管器件的电压到达开启电压后，由阴极产生的电子经电子传输层传输到阳极，相反地,空穴不能从阳极注入。仅电子有机半导体二极管器件中的电子传输材料可应用到其它半导体器件如有机电致发光器件。有机电致发光器件市场庞大，因而稳定、高效的有机电子传输材料对有机电致发光器件的应用和推广具有重要作用，同时也是有机电致发光大面积面板显示的应用推广的迫切需求。
市场上现有较多使用的电子传输材料向红菲咯啉(bathophenanthroline,BPhen)和浴铜灵(bathocuproine,BCP)，基本上能符合有机电致发光面板的市场需求，但其效率和稳定性仍有待进一步提高。从BPhen及BCP的分子结构中分析(见下式，分子结构的镜面用虚线表示)，其对称结构会使分子倾向有规则地堆叠，时间过后容易做成结晶。电子传输材料一旦结晶，分子间的电荷跃迁机制跟在正常运作的非晶态薄膜机制不相同，引致电子传输性能改变。如果BPhen对称分子结构的材料在有机电致发光器件中使用，时间过后会使整个器件导电性能改变，令电子和空穴电荷迁移率失衡，引致到器件效能下降，也可能会在器件中产生局部短路，影响器件稳定性，甚至令器件失效。(参考文献Journal of Applied Physics 80,2883(1996)；doi:10.1063/1.363140)
发明内容
针对上述材料的缺陷，本发明提供一种可应用在长寿命仅电子有机半导体二极管器件和有机电致发光器件中的高形态稳定性的有机电子传输材料。
高Tg有机电子传输材料，具有式(I)所述的结构，
其中，9,9'-螺二芴连接位置为1-,2-,3-,或4-位；其中，Ar1、Ar2独立地表示为未取代或者C1-C6取代的C6-C25芳基。
优选：Ar1，Ar2独立地表示为C1-C5烷基取代或者苯基取代或者未取代的苯基、萘基、蒽基，菲基，芘基，苝基，荧蒽基，(9,9-二烷基取代或未取代芳基)芴基或9,9-螺芴基。
优选：其中，9,9'-螺二芴连接位置为2-或4-位；其中，Ar1、Ar2独立地表示为苯基，甲苯基，二甲苯基，萘基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，(9,9-二烷基)芴基，(9,9-二甲基取代或未取代苯基)芴基，9,9-螺芴基。
优选：Ar1、Ar2表示为苯基。
优选：9,9'-螺二芴连接位置为2-或4-位；式(I)所述的化合物为下列结构化合物：
高Tg有机电子传输材料的制备方法，包括如下步骤：
(1)溴代9,9'-螺二芴与正丁基锂反应，生成9,9'-螺二芴锂，
(2)9,9'-螺二芴锂与式(II)反应后加水，再于空气中温室搅拌20－30小时得目标产物。
所述步骤(1)的反应条件为：向溶有溴代9,9'-螺二芴的无水四氢呋喃溶液中，缓慢滴加正丁基锂的正己烷溶液(42mL,1.25M)，反应温度-90－-80℃下。
所述步骤(2)的9,9'-螺二芴锂与式(II)的反应条件为：于-90－-80℃下在步骤(1)的反应混合物中滴加溶有式(II)的无水四氢呋喃溶液，滴完后室温搅拌，6－10小时。
步骤(2)后还包括目标产物的提取和纯化，所述提取和纯化方法为将反应混合物蒸干溶剂，加入水和乙酸乙酸，合并有机层，加干燥剂干燥，再将有机层中溶剂旋干，丙酮打浆，抽滤，滤质为纯化的目标产物。
本发明材料可用于仅电子有机半导体二极管器件，包含阳极，阴极，和有机层，所述阳极和阴极为金属、无机物或有机化合物；所述有机层为空穴阻挡层、电子传输层、电子注入层中的一层或多层；所述电子传输层为由电子传输材料组成，所述电子传输材料具有式(I)所述结构的化合物。需要特别指出，上述有机层可以根据需要，这些有机层不必每层都存在。
所述空穴传挡层，电子传输层和/或电子注入层中含有式(I)所述的化合物，所述式(I)所述的化合物为空穴阻挡材料，电子传输材料，和电子注入材料。
其中有机层的总厚度为1-1000nm，优选1-500nm，更优选5-300nm。所述有机层为空穴注入层，空穴传输层，发光层，空穴阻挡层、电子传输层、电子注入层中的一层或多层。需要特别指出，上述有机层可以根据需要，这些有机层不必每层都存在。
所述空穴传输层，电子传输层和/或发光层中含有式(I)所述的化合物。
所述有机层可以通过蒸渡或旋涂形成薄膜。
本发明材料也可用于有机电致发光器件，其中有机层的总厚度为1-1000nm，优选1-500nm，更优选50-300nm。
本发明的有机电致发光器件包括有一层或多层发光层，发光层中含有本发明的式(I)所述的化合物。
所述发光层为由主体材料和客体材料组成的主客体掺杂体系或单一发光材料体系。
如上面提到的，本发明的式(I)所述的化合物如下，但不限于所列举的结构：
材料实验表明，本发明式(I)所述的化合物具有高玻璃化转变温度，因此证明本发明式(I)所述的化合物有高形态稳定性的有机材料。器件实验表明，使用本发明的有机电子传输材料制备的仅电子有机半导体二极管器件及有机电致发光器件性能良好且稳定，器件寿命长。
图1为本发明的器件结构图，
其中10代表为玻璃基板，20代表为阳极，30代表为空穴阻挡层，40代表为电子传输层，50代表为电子注入层，60代表为阴极。
图2为化合物2的1H NMR图。
图3为化合物2的13C NMR图。
图4为化合物2的HPLC图。
图5为化合物2的TGA图。
图6为化合物2的DSC图。
图7为实施例2,实施例3,实施例4的电流密度与电场强度关系图，
图8为比较例1,比较例2的电流密度与电场强度关系图。
为了更详细叙述本发明，特举以下例子，但是不限于此。
实施例1
化合物2的合成
反应投放：3L三口反应瓶，装配磁力搅拌及低温温度计，氮气排空3次，加入2-溴-9,9'-螺二芴(20.0g,50.6mmol)，无水四氢呋喃(1000mL)，搅拌至溶解，液氮/乙醇浴冷却至-90～-80℃，缓慢滴加正丁基锂的正己烷溶液(42mL,1.25M)，控制反应温度-75℃以下，
正丁基锂全部滴加完毕后，继续反应0.5h，而后滴加4,7-二苯基菲罗啉(25.0g,75mmol)/THF溶液(1000mL)，控制温度-75℃以下，滴加完毕后，加入溶液后室温搅拌8h，加水(10mL)然后在空气中搅拌24h。停止反应后，旋干THF，加入水和乙酸乙酯萃取，有机层合并，用无水硫酸镁干燥后过滤，滤液旋干后用丙酮打浆，抽滤，滤质为含化合物2(12.46g,产率38.1％,HPLC纯度99.2％)。7.40g粗产品在真空(4x 10-5torr)加热320℃升华完成后得到5.11g淡黄色粉末状产品，纯度99.5％。
实施例2
仅电子有机半导体二极管器件1的制备
使用本发明实施例1的化合物作为有机电子传输材料制备仅电子有机半导体二极管器件，见图1所示。
首先，将透明导电ITO玻璃基板10(上面带有阳极20)依次经：洗涤剂溶液和去离子水，乙醇，丙酮，去离子水洗净，再用氧等离子处理30秒。
然后，在ITO上蒸渡5nm厚的BCP作为空穴阻挡层30。
然后，在空穴阻挡层上蒸渡100nm厚的化合物2作为电子传输层40。
然后，在电子传输层上蒸渡1nm厚的氟化锂作为电子注入层50。
最后，在电子注入层上蒸渡100nm厚的铝作为器件阴极60。
通过利用空间限制电流(space charge limited current,SCLC)电流密度与电场强度的关系如式(1)：
其中，J为电流密度(mA cm-2),ε为相对介电常数(有机材料通常取值为3)，ε0为真空介电常数(8.85×10-14C V-1cm-1)，E为电场强度(V cm-1)，L为器件中样本的厚度(cm)，μ0为零电场下的电荷迁移率(cm2V-1s-1)，β为Poole–Frenkel因子，表示迁移率随电场强度变化的快慢程度。
所制备的器件在E＝1x 106Vcm-1的工作电场下的电子迁移率为4.25x 10-4cm2V-1s-1。
器件中所述结构式
实施例3
仅电子有机半导体二极管器件2的制备
与仅电子有机半导体二极管器件1的制备一样,作为重复验证数据。
实施例4
仅电子有机半导体二极管器件3的制备
与仅电子有机半导体二极管器件1的制备一样,作为重复验证数据。
比较例1
仅电子有机半导体二极管器件4的制备
方法同实施例2，但使用常用市售化合物TmPyPB作为电子传输层40，制作对比用仅电子有机半导体二极管器件。
所制备的器件在E＝1x 106Vcm-1的工作电场下的电子迁移率为1.34x 10-5cm2V-1s-1。
器件中所述结构式
比较例2
仅电子有机半导体二极管器件5的制备
与仅电子有机半导体二极管器件4的制备一样,作为重复验证数据。
比较材料的玻璃化转变温度:
比较器件1-3及4-5数据表明材料化合物2比常用的TmPyPB在相同的工作电场下的电子迁移率高出30倍，玻璃化转变温度高出3倍，因为器件寿命和材料的玻璃化转变温度有关，材料的玻璃化转变温度越高,器件稳定性越好寿命越长,因此本发明的材料是一种可应用在长寿命仅电子有机半导体二极管器件和有机电致发光器件中的高形态稳定性的有机电子传输材料。
Claims (10)
- 高Tg有机电子传输材料，具有式(I)所述的结构，
其中，9,9'-螺二芴连接位置为1-,2-,3-,或4-位；其中，Ar1、Ar2独立地表示为未取代或者C1-C6取代的C6-C25芳基。 - 根据权利要求1所述的高Tg有机电子传输材料，其中，Ar1，Ar2独立地表示为C1-C5烷基取代或者苯基取代或者未取代的苯基、萘基、蒽基，菲基，芘基，苝基，荧蒽基，(9,9-二烷基取代或未取代芳基)芴基或9,9-螺芴基。
- 根据权利要求2所述的高Tg有机电子传输材料，其中Ar1、Ar2独立地表示为苯基，甲苯基，二甲苯基，萘基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，(9,9-二烷基)芴基，(9,9-二甲基取代或未取代苯基)芴基，9,9-螺芴基。
- 根据权利要求3所述的高Tg有机电子传输材料，其中Ar1、Ar2表示为苯基。
- 根据权利要求4所述的高Tg有机电子传输材料，9,9'-螺二芴连接位置为2-或4-位；式(I)所述的化合物为下列结构化合物：
- 权利要求1－5任一高Tg有机电子传输材料的制备方法，包括如下步骤：(1)溴代9,9'-螺二芴与正丁基锂反应，生成9,9'-螺二芴锂，(2)9,9'-螺二芴锂与式(II)反应后加水，再于空气中温室搅拌20－30小时得目标产物。
- 根据权利要求6所述的方法，所述步骤(1)的反应条件为：向溶有溴代9,9'-螺二芴的无水四氢呋喃溶液中，缓慢滴加正丁基锂的正己烷溶液(42mL,1.25M)，反应温度-90－-80℃下。
- 根据权利要求7所述的方法，所述步骤(2)的9,9'-螺二芴锂与式(II)的反应条件为：于-90－-80℃下在步骤(1)的反应混合物中滴加溶有式(II)的无水四氢呋喃溶液，滴完后室温搅拌，6－10小时。
- 根据权利要求8所述的方法，步骤(2)后还包括目标产物的提取和纯化，所述提取和纯化方法为将反应混合物蒸干溶剂，加入水和乙酸乙酸，合并有机层，加干燥剂干燥，再将有机层中溶剂旋干，丙酮打浆，抽滤，滤质为纯化的目标产物。
- 权利要求1－5任一高Tg有机电子传输材料在仅电子有机半导体二极管器件及有机电致发光器件中的应用。
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112951A (zh) * | 1994-04-07 | 1995-12-06 | 赫彻斯特股份公司 | 螺环化合物及其作为电荧光材料的应用 |
| JP2004303489A (ja) * | 2003-03-28 | 2004-10-28 | Tdk Corp | 有機ｅｌ素子及び有機ｅｌディスプレイ |
| CN1678561A (zh) * | 2002-08-01 | 2005-10-05 | 科文有机半导体有限公司 | 螺二芴衍生物、其制备和用途 |
| CN101076904A (zh) * | 2004-11-24 | 2007-11-21 | 普林斯顿大学理事会 | 具有菲咯啉激子阻挡层的有机光敏光电器件 |
| CN101121715A (zh) * | 2005-08-11 | 2008-02-13 | 株式会社半导体能源研究所 | 菲咯啉衍生物化合物 |
| CN101978528A (zh) * | 2008-01-30 | 2011-02-16 | 全球Oled科技有限责任公司 | 具有双空穴阻挡层的磷光有机发光器件 |
| JP2014133727A (ja) * | 2013-01-11 | 2014-07-24 | Canon Inc | 表示装置及び表示装置の製造方法、並びにこの表示装置の製造方法で用いられる有機化合物 |
| CN104403661A (zh) * | 2014-11-07 | 2015-03-11 | 烟台万润精细化工股份有限公司 | 一种有机电致发光材料及其应用 |
| CN105176517A (zh) * | 2015-04-23 | 2015-12-23 | 长春理工大学 | 一种不含重金属元素的光学氧传感复合材料及其制备方法 |
| EP3032599A1 (en) * | 2014-12-12 | 2016-06-15 | Solvay SA | Organic semiconductor composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4750595B2 (ja) * | 2006-03-28 | 2011-08-17 | キヤノン株式会社 | 有機発光素子アレイ |
| KR102197165B1 (ko) * | 2011-07-29 | 2021-01-04 | 메르크 파텐트 게엠베하 | 전자 소자용 화합물 |
| KR101781569B1 (ko) * | 2012-06-06 | 2017-09-26 | 광동 어글레이어 압토일렉트라닉 머티어리얼즈 컴퍼니 리미티드 | 유기 전자재료와 유기전기 발광소자 |
-
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-
2017
- 2017-05-26 TW TW106117610A patent/TWI640523B/zh active
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Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112951A (zh) * | 1994-04-07 | 1995-12-06 | 赫彻斯特股份公司 | 螺环化合物及其作为电荧光材料的应用 |
| CN1678561A (zh) * | 2002-08-01 | 2005-10-05 | 科文有机半导体有限公司 | 螺二芴衍生物、其制备和用途 |
| JP2004303489A (ja) * | 2003-03-28 | 2004-10-28 | Tdk Corp | 有機ｅｌ素子及び有機ｅｌディスプレイ |
| CN101076904A (zh) * | 2004-11-24 | 2007-11-21 | 普林斯顿大学理事会 | 具有菲咯啉激子阻挡层的有机光敏光电器件 |
| CN101121715A (zh) * | 2005-08-11 | 2008-02-13 | 株式会社半导体能源研究所 | 菲咯啉衍生物化合物 |
| CN101978528A (zh) * | 2008-01-30 | 2011-02-16 | 全球Oled科技有限责任公司 | 具有双空穴阻挡层的磷光有机发光器件 |
| JP2014133727A (ja) * | 2013-01-11 | 2014-07-24 | Canon Inc | 表示装置及び表示装置の製造方法、並びにこの表示装置の製造方法で用いられる有機化合物 |
| CN104403661A (zh) * | 2014-11-07 | 2015-03-11 | 烟台万润精细化工股份有限公司 | 一种有机电致发光材料及其应用 |
| EP3032599A1 (en) * | 2014-12-12 | 2016-06-15 | Solvay SA | Organic semiconductor composition |
| CN105176517A (zh) * | 2015-04-23 | 2015-12-23 | 长春理工大学 | 一种不含重金属元素的光学氧传感复合材料及其制备方法 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232153A (zh) * | 2021-04-23 | 2022-10-25 | 江苏三月科技股份有限公司 | 一种含有萘和1,10-菲啰啉结构的有机化合物及包含其的oled发光器件 |
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