CN106188145B - 一种锰(ii)配合物及其制备方法和在有机发光二极管中的用途 - Google Patents
一种锰(ii)配合物及其制备方法和在有机发光二极管中的用途 Download PDFInfo
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- CN106188145B CN106188145B CN201610487014.XA CN201610487014A CN106188145B CN 106188145 B CN106188145 B CN 106188145B CN 201610487014 A CN201610487014 A CN 201610487014A CN 106188145 B CN106188145 B CN 106188145B
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- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000010668 complexation reaction Methods 0.000 title description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 12
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 12
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- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 claims description 2
- FQJQNLKWTRGIEB-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-[3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C(C)(C)C)O1 FQJQNLKWTRGIEB-UHFFFAOYSA-N 0.000 claims description 2
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- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims 1
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
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- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
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- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 2
- XNCMQRWVMWLODV-UHFFFAOYSA-N 1-phenylbenzimidazole Chemical class C1=NC2=CC=CC=C2N1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 1
- 229910021574 Manganese(II) iodide Inorganic materials 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- XHVNHWZODMMDEW-UHFFFAOYSA-N iridium(3+);phosphane Chemical compound P.[Ir+3] XHVNHWZODMMDEW-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种廉价的锰(II)配合物及其制备方法和用途，所述配合物的结构为：(R1R2R3R4A)2[MnX4]，其中，R1、R2、R3和R4相同或不同，独立的选自：烷基、芳基、杂芳基，上述所述烷基、芳基、杂芳基可以任选被取代基取代，所述取代基优选为烷基、芳基、杂芳基；A为N、P、或As；X任选为：F、Cl、Br、或I。本发明还涉及了一种有机发光二极管及其制备方法和用途，以本发明所述的锰(II)配合物为发光层掺杂体，制备得到的有机发光二极管，具有高性能的有机电致发光，可应用于平板显示和照明。
Description
技术领域
本发明属于有机发光二极管电致发光领域，可应用于彩色平板显示和照明领域。具体涉及一种绿光发射的锰(II)配合物及其制备方法，该配合物可用于有机发光二极管。
背景技术
有机电致发光是有机发光二极管(OLED)在3-12V低直流电压作用下将电能直接转化为光能的发光现象，它在平板显示和照明领域具有非常广阔的应用。与传统照明和显示技术相比，有机电致发光具有全彩色显示、广视角、高清晰、快速响应、低功耗、高效率、耐低温等诸多优点；而且有机发光器件具有结构简单、超轻、超薄、柔性可折叠等优异特性。
有机发光二极管的核心是发光薄膜材料，目前商用有机电致发光器件所用的磷光材料绝大多数是电中性环金属铱(III)配合物，将其掺杂于有机主体材料中组成发光层。当前制约有机发光二极管大规模商业应用的主要瓶颈有三点。(1)铱是贵金属，地球含量非常有限，是地球储量最少的金属元素之一，全世界每年仅生产三吨；(2)采用真空热蒸镀法制备中性环金属铱(III)配合物发光层导致较高的制备成本，且难于生产大面积器件；(3)蓝光器件的稳定工作时间有待增长。针对这些挑战，本发明采用地球储量丰富、廉价和环境友好的金属锰(II)发光材料取代贵金属铱(III)磷光材料，获得了高性能的廉价绿光有机发光二极管。
发明内容
本发明的目的是提供一类锰(II)配合物及其在有机发光二极管中的用途。
本发明的另一目的是提供一种含有上述锰(II)配合物的有机发光二极管。
本发明的目的通过如下方式实现：
一种锰(II)配合物，其结构为：(R1R2R3R4A)2[MnX4]；
其中，R1、R2、R3和R4相同或不同，独立的选自：烷基、芳基、杂芳基，上述所述烷基、芳基、杂芳基可以任选被取代基取代，所述取代基优选为烷基、芳基、杂芳基；
A为：N、P、或As；
X任选为：F、Cl、Br、或I。所述的烷基是指具有1-10(优选1-6)个碳原子的直链和支链烷基，代表性的烷基包括：甲基、乙基、正丙基、异丙基、正丁基、叔丁基等。
所述的芳基是指具有6-20个碳原子的单环、多环芳族基团，代表性的芳基包括：苯基、萘基等。
所述的杂芳基是指具有1-20个碳原子、并且包含至少1个，优选1-4个选自N、S、O杂原子的单环或多环杂芳族基团，代表性的杂芳基包括：吡咯基、吡啶基、嘧啶基、咪唑基、噻唑基、噁唑基、噁二唑基、咔唑基、喹啉基、喹唑啉基、吲哚基等。
根据本发明，所述锰(II)配合物的结构为如下式(I)所示：
在一个实施方式中，当A为N时，R1、R2、R3和R4不能同时为丁基。
根据本发明，优选的，R1、R2、R3和R4独立的选自：烷基、芳基、芳基烷基、杂芳基、芳基杂环基。更优选的，R1、R2、R3和R4独立的选自：乙基、正丁基、苯基、卞基、咔唑基、苯基咔唑基。
在一个实施方式中，R1与R2相同，R3与R4相同。
在又一个实施方式中，R1、R2、R3和R4均相同。
根据本发明，优选的，A为N、或P。
根据本发明，所述锰(II)配合物选自如下具体化合物：
化合物1：R1、R2、R3和R4相同，且为苯基；A为P；X为Cl；
化合物2：R1、R2、R3和R4相同，且为苯基；A为P；X为Br；
化合物3：R1、R2、R3和R4相同，且为苯基；A为P；X为I；
化合物4：R1和R2相同，且为9-咔唑基；R3和R4相同，且为苯基；A为P；X为Br；
化合物5：R1、R2、R3和R4相同，且为正丁基；A为N；X为Br。
本发明还提供了一种制备所述锰(II)配合物的制备方法，包括如下步骤：将MnX2和(R1R2R3R4A)X在溶剂中混合，得到所述锰(II)配合物，其中，R1、R2、R3、R4、A、和X如上所定义。
根据本发明，所述溶剂优选为醇或卤代烃，例如甲醇或二氯甲烷。
根据本发明，在所述方法中，MnX2：(R1R2R3R4A)X的摩尔比为1.5～2.5:0.5～1.5，优选摩尔比为1:2。
根据本发明，所述反应在室温下进行。优选的，反应结束后，用重结晶提纯。重结晶所用溶剂优选为石油醚和二氯甲烷。
本发明的锰(II)配合物在溶液、晶体和薄膜状态中均具有很强的磷光发射。其可以作为发光层掺杂体，用于有机发光二极管中。
本发明还提供了所述锰(II)配合物的用途，其用于有机发光二极管中。
进一步的，本发明还提供了一种有机发光二极管，其包括发光层，所述发光层中含有本发明所述的锰(II)配合物。有机发光二极管具有高性能的电致绿光发射。
根据本发明，在所述发光层中，本发明所述的锰(II)配合物占所有材料的0-50％(重量百分比)，优选10-30％，进一步优选的，本发明所述的锰(II)配合物以20％的重量百分比掺杂到主体材料中作为发光层。
根据本发明，所述有机发光二极管的结构可以为现有技术中已知的各种结构。优选的包括：阳极层、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极层。所述有机发光二极管还进一步包括基板(例如玻璃基板)。所述阳极层可为铟锡氧化物。所述空穴注入层、空穴传输层可为PEDOT:PSS(PEDOT:PSS＝聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸))。所述发光层含有本发明所述的锰(II)配合物，以及具有空穴传输特性的物质，例如选自TCTA(三(4-(9-咔唑)苯基)胺)、mCP(1,3-双(9-咔唑基)苯)、CBP(4,4'-二(9-咔唑)-1,1'-联苯)、或2,6-DCZPPY(2,6-二(3-(9-咔唑)苯基)吡啶)中的一种或多种。所述电子传输层可为TPBi(1,3,5-三(1-苯基-1H-苯并[d]咪唑-2-基)苯)、BmPyPB(3,3”,5,5”-四(3-吡啶基)-1,1':3',1”-三联苯)、BCP(2,9-二甲基-4,7-二苯基-1,10-菲珞啉)或OXD-7(2,2'-(1,3-苯基)二[5-(4-叔丁基苯基)-1,3,4-恶二唑])。所述电子注入层为LiF。所述阴极层为Al。
根据本发明，所述器件结构优选为：ITO/PEDOT:PSS(50nm)/40％TCTA:40％2,6-DCZPPY:20％wt本发明的锰(II)配合物(50nm)/TPBi(50nm)/LiF(1nm)/Al(100nm)，其中ITO为铟锡氧化物导电薄膜，PEDOT:PSS为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)，TCTA为三(4-(9-咔唑)苯基)胺，2,6-DCZPPY为2,6-二(3-(9-咔唑)苯基)吡啶，TPBi为1,3,5-三(1-苯基-1H-苯并[d]咪唑-2-基)苯。
本发明还提供了一种制备所述有机发光二极管的方法，包括：1)采用溶液法在阳极上制备有机发光二极管中的空穴注入层/空穴传输层；2)采用溶液法制备掺杂有本发明的锰(II)配合物的发光层；3)再依次利用真空热蒸镀方法制备电子传输层、电子注入层、以及阴极层。
在一个优选的实施方式中，所述方法包括：首先利用水溶性PEDOT:PSS在阳极上制备空穴注入层和空穴传输层；再利用具有空穴传输特性的TCTA和2,6-DCZPPY为混合主体材料，与本发明所述的锰(II)配合物掺杂制备发光层；再依次利用真空热蒸镀方法制备TPBi电子传输层、LiF电子注入层、以及Al阴极层。
根据本发明，在所述方法中，PEDOT:PSS空穴注入层/空穴传输层和掺杂本发明所述的锰(II)配合物的TCTA：2,6-DCZPPY发光层分别利用溶液旋涂法制备薄膜，TPBi电子传输层和LiF电子注入层采用真空热蒸镀法制备薄膜。
由本发明的磷光锰(II)配合物制备的有机发光二极管具有优异的性能，其具有相当高的电-光转换效率，最大量子效率大于2％。
本发明进一步提供了所述有机发光二极管的用途，其可以用于平板显示和日常照明领域中。
与现有技术相比，本发明具有如下优点：
1)本发明的磷光锰(II)配合物在固体和薄膜中均具有很强的磷光发射，其薄膜磷光量子效率高于20％；
2)本发明采用廉价磷光锰(II)配合物替代贵金属铱(III)配合物为发光层掺杂体制备的有机发光二极管，大幅度降低了发光材料制备成本；
3)本发明利用溶液法制备有机发光二极管的空穴注入层/空穴传输层和发光层，能够大幅度降低器件制备成本。
附图说明：
图1为器件结构示意图及有机材料化学结构图。
具体实施方式：
为了使本发明的发明目的、技术方案和技术效果更加清晰，以下结合附图和实施例对本发明进行进一步详细说明。但本领域技术人员了解，下述实施例不是对本发明保护范围的限制。任何在本发明基础上做出的改进和变化，都在本发明的保护范围之内。
实施例1：配合物(Ph4P)2[MnCl4](1)的制备
向10mL溶解了无水MnCl2(47.3mg,0.1mmol)的甲醇溶液中加入10毫升Ph4PCl(50.6mg,0.2mmol)的甲醇溶液。在室温下搅拌4小时,将反应液真空抽干。所得固体用5mL二氯甲烷溶解，过滤，得透明滤液。在室温下将石油醚缓慢扩散到二氯甲烷溶液中进行重结晶，得到淡绿色晶体。产率：92％。元素分析(C48H40Cl4P2Mn)计算值:C,65.85；H,4.60。测量值:C,65.56；H,4.57。红外光谱(KBr,cm-1):3843,3741,3633,3517,3057,1625,1586,1484,1437,1315,1111,993,766,727,687,527。
实施例2：配合物(Ph4P)2[MnBr4](2)的制备
制备方法与实施例1中方法基本相同，仅是使用无水MnBr2替代无水MnCl2，并用Ph4PBr替代Ph4PCl。产率:95％.元素分析(C48H40Br4P2Mn)计算值:C,54.73；H,3.83。测量值:C,54.25；H,3.78。红外光谱(KBr,cm-1):3850,3736,3473,3051,1621,1587,1483,1107,996,758,724,692,528。
实施例3：配合物(Ph4P)2[MnI4](3)的制备
制备方法与实施例1中方法基本相同，仅是使用无水MnI2替代无水MnCl2，并用Ph4PI替代Ph4PCl。产率:75％。元素分析(C48H40I4P2Mn)计算值:C,46.40；H,3.25。测量值:C,46.90；H,3.28。红外光谱(KBr,cm-1):3847,3454,3057,1625,1585,1485,1437,1385,1313,1110,997,759,724,689,526,448。
实施例4：配合物{Ph2P(咔唑-9)2}2[MnBr4](4)的制备
制备方法与实施例2中方法基本相同，仅是使用合成的Ph2P(咔唑-9)2Br替代无水PPh4Br。产率:78％。元素分析(C72H54Br4N2P2Mn)计算值:C,62.50；H,3.93；N,2.02。测量值:C,65.26；H,3.90；N,2.11。红外光谱(KBr,cm-1):3860,3754,3470,3055,1628,1581,1484,1422,1391,1112,998,757,729,671,526。
实施例5：配合物[(n-Bu)4N]2[MnBr4](5)的制备
制备方法与实施例2中方法基本相同，仅是使用(n-Bu)4NBr替代无水PPh4Br。产率:87％。元素分析(C32H72Br4N2Mn)计算值:C,44.72；H,8.44；N,3.26。测量值:C,44.56；H,8.26；N,3.38。红外光谱(KBr,cm-1):3465,3423,2958,2868,1486,1387,1155,1033,873,747。
实施例6：光致发光性能测试
在Edinburgh FLS920荧光光谱仪上分别测试实施例1-5中制备的配合物1-5晶体及40％TCTA:40％2,6-DCZPPY:20％实施例1-5中的锰(II)配合物1-5(重量比)薄膜的激发光谱、发射光谱、发光寿命和发光量子产率。利用直径为142mm的积分球测定晶体样品的发光量子产率。将二氯甲烷溶液旋涂的40％TCTA:40％2,6-DCZPPY:20％实施例1-5中的锰(II)配合物1-5(重量比)薄膜置于直径为142mm的积分球测定薄膜的发光量子产率。
实施例1-5中的配合物1-5在晶体和薄膜中均具有很强的磷光发射。发射波长、发光寿命和量子产率列于表1。
表1.本发明配合物1-5光致发光发射波长、发光寿命和量子产率
实施例7：有机发光二极管器件制备与电致发光性能测试
分别利用实施例1-5中制备的磷光配合物1-5为发光材料以20％的重量百分比掺杂到TCTA(40％):2,6-DCZPPY(40％)混合主体材料中作为发光层制备有机发光二极管，器件结构为：ITO/PEDOT:PSS(50nm)/40％TCTA:40％2,6-DCZPPY:20％实施例1-5中锰(II)配合物1-5(50nm)/TPBi(50nm)/LiF(1nm)/Al(100nm)。
首先分别利用去离子水、丙酮、异丙醇清洗ITO基底，再采用UV-臭氧处理15分钟。将过滤后的PEDOT:PSS水溶液在旋涂仪上以3000转/分钟的转速旋涂到ITO基底上，在140℃干燥20分钟后得到50nm厚度的空穴注入层/空穴传输层。再利用旋涂仪将过滤后的浓度为40％TCTA:40％2,6-DCZPPY:20％实施例1-5中锰(II)配合物1-5(重量百分比)的二氯甲烷溶液以1500转/分钟的转速旋涂到PEDOT:PSS薄膜上形成50nm厚度的发光层。随后，将ITO基底置于真空度不低于4×10-4Pa的真空腔中，依次热蒸镀50nm厚的TPBi电子传输层、1nm厚的LiF电子注入层、以及100nm厚度的Al为器件阴极。
发光二极管器件性能测试在室温干燥的空气环境中进行。实施例1-5制备的锰(II)配合物1-5的电致发光性能参数包括电致发光波长(λEL)，启亮电压(Von)，最大亮度(Lmax)，最大电流效率(CEmax)，最大功率效率(PEmax)，最大外量子效率(EQEmax)列于表2。
表2.本发明磷光锰(II)配合物1-5电致发光器件性能数据
a)亮度为1cd/m2的启亮电压，b)最大亮度，c)最大电流效率，d)最大功率效率，e)最大外量子效率。
Claims (16)
1.一种锰(II)配合物，其结构为：(R1R2R3R4A)2[MnX4]， 其中：R1和R2相同，且为9-苯基咔唑基；R3和R4相同，且为苯基；A为P；X为Br ；
。
2.一种权利要求1所述的锰(II)配合物的制备方法，包括如下步骤：将MnX2和(R1R2R3R4A)X在溶剂中混合，得到所述锰(II)配合物，其中，R1、R2、R3、R4、A、X如权利要求1所定义。
3.锰(II)配合物用于有机发光二极管的用途，其中，所述锰(II)配合物的结构为：(R1R2R3R4A)2[MnX4]，
其中，R1、R2、R3和R4相同或不同，独立的选自：芳基、杂芳基，上述所述芳基、杂芳基可以任选被取代基取代，所述取代基为烷基、芳基、杂芳基；
A为：N、P、或As；
X任选为：F、Cl、Br、或I；
所述的烷基是指具有1-10个碳原子的直链或支链烷基，所述的芳基是指具有6-20个碳原子的单环、多环芳族基团，所述的杂芳基是指具有1-20个碳原子、且包含至少1个选自N、S、O杂原子的单环或多环杂芳族基团。
4.根据权利要求3所述的用途，其中，R1、R2、R3和R4独立的选自：芳基、杂芳基、芳基杂芳基。
5.根据权利要求4所述的用途，其中，R1、R2、R3和R4独立的选自：苯基、咔唑基、苯基咔唑基。
6.根据权利要求4所述的用途，其中，A为N、或P。
7.根据权利要求4所述的用途，其中，所述配合物选自如下具体化合物：
化合物1：R1、R2、R3和R4相同，且为苯基；A为P； X为Cl；
化合物2：R1、R2、R3和R4相同，且为苯基；A为P；X为Br；
化合物3：R1、R2、R3和R4相同，且为苯基；A为P； X为I；
化合物4：R1和R2相同，且为9-苯基咔唑基；R3和R4相同，且为苯基；A为P；X为Br。
8.一种有机发光二极管，包括发光层，其中，所述发光层中含有如权利要求3-7任一项中所述的配合物。
9.根据权利要求8所述的有机发光二极管，其中，在所述发光层中，权利要求3-7任一项中所述的配合物占所有材料的重量百分比为5-50%。
10.根据权利要求9所述的有机发光二极管，其中，在所述发光层中，权利要求3-7任一项中所述的配合物占所有材料的10-30%。
11.根据权利要求8所述的有机发光二极管，其中所述有机发光二极管包括：阳极层、空穴注入层/空穴传输层、发光层、电子传输层、电子注入层和阴极层。
12.根据权利要求11所述的有机发光二极管，其中，所述阳极层为铟锡氧化物；所述空穴注入层、空穴传输层为PEDOT : PSS；所述发光层含有权利要求3-7中任一项所述的配合物，以及具有空穴传输特性的物质；所述电子传输层为TPBi，BmPyPB，BCP或OXD-7；所述电子注入层为LiF；所述阴极层为Al。
13.根据权利要求12所述的有机发光二极管，其中，所述空穴传输特性的物质选自TCTA、mCP、CBP或2,6-DCZPPY中的一种或多种。
14.根据权利要求12所述的有机发光二极管，其中，器件结构为：ITO / PEDOT : PSS /40% TCTA : 40% 2,6-DCZPPY : 20% wt权利要求3-7任一项中所述的锰(II)配合物/ TPBi/ LiF / Al。
15.一种制备权利要求8-14任一项所述的有机发光二极管的方法，包括：1）采用溶液法在阳极层上制备有机发光二极管中的空穴注入层、空穴传输层；2）采用溶液法制备掺杂有权利要求3-7任一项中所述配合物的发光层；3）再依次利用真空热蒸镀方法制备电子传输层、电子注入层、以及阴极层。
16.权利要求8-14任一项所述的有机发光二极管的用途，其可以用于平板显示和日常照明领域中。
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| KR1020187036704A KR102181449B1 (ko) | 2016-06-28 | 2017-05-19 | 망간(ii) 착물과 그 제조방법 및 유기발광 다이오드에서의 용도 |
| PCT/CN2017/085149 WO2018000984A1 (zh) | 2016-06-28 | 2017-05-19 | 一种锰(ii)配合物及其制备方法和在有机发光二极管中的用途 |
| EP17818981.7A EP3476855B1 (en) | 2016-06-28 | 2017-05-19 | Manganese (ii) complex, preparation method therefor, and application of same in organic light emitting diode |
| US16/313,863 US11279721B2 (en) | 2016-06-28 | 2017-05-19 | Manganese (II) complex, preparation method thereof, and use thereof in organic light emitting diodes |
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