CN104387369B - 一种热激活延迟荧光材料的合成方法及其应用 - Google Patents
一种热激活延迟荧光材料的合成方法及其应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 25
- 230000003111 delayed effect Effects 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title 1
- 238000007725 thermal activation Methods 0.000 title 1
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000004913 activation Effects 0.000 claims description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- -1 carbazole compound Chemical class 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000005401 electroluminescence Methods 0.000 claims 2
- 238000002347 injection Methods 0.000 claims 2
- 239000007924 injection Substances 0.000 claims 2
- 230000027756 respiratory electron transport chain Effects 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HJCUTNIGJHJGCF-UHFFFAOYSA-N 9,10-dihydroacridine Chemical compound C1=CC=C2CC3=CC=CC=C3NC2=C1 HJCUTNIGJHJGCF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JXISJBVJNUKKBK-UHFFFAOYSA-N 2,3,5,6-tetrafluoropyridine-4-carbonitrile Chemical class FC1=NC(F)=C(F)C(C#N)=C1F JXISJBVJNUKKBK-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Engineering & Computer Science (AREA)
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Abstract
本发明开发了一种原料廉价易得，无需加入贵金属催化剂，操作简便，反应条件温和，生产成本低，产率高，便于商业化的一步法合成氰基吡啶和咔唑类化合物的方法，涉及有机电致发光材料领域，具体涉及一步法合成一种热激活延迟荧光材料及将其作为OLED器件的发光层。
Description
技术领域
本发明涉及有机电致发光材料领域，特别涉及一种热激活延迟荧光材料、一步法的合成方法及使用该热激活延迟荧光材料的OLED器件。
技术背景
有机发光二极管(OLED)在大面积、高分辨率平板显示方面具有巨大潜能，在过去20年，基于单线态发光的荧光OLED作为第一代发光材料其理论上的内量子效率只有25％，无法进一步提高其效率；磷光OLED被称为第二代，其内量子效率能达到100％，但其存在稳定性差寿命短的问题，而且蓝光磷光是一直需要解决的问题。2009年，日本九州大学的Adachi教授发现了基于三线态-单线态跃迁的热激活延迟荧光(TADF)新材料，其内量子效率接近100％，这类材料被称为第三代OLED高效发光材料。它来源于从第一激发三重态(T1)重新生成的S1态的辐射跃迁，内量子效率可达到100％，这类材料能具有长寿命、色纯度高、成本低等优点。然而目前这一类新材料还较少，有待研究人员进一步开发研亢。
2014年最新一期Nature Photonics，Chilhaya Adachi等[Qisheng Zhang，BoLi，Shuping Huang，Hiroko Nomura，Hiroyuki Tanaka and Chihaya Adachi.DIO：10.1038/NPHOTO.2014.12]报道了一类二氢吖啶和二苯基砜化合物作为蓝光延迟荧光材料外量子效率(EQE)达到了19.5％，完全可与磷光材料相媲美。
发明内容
本发明的目的在于提供一种热激活延迟荧光材料，其结合了多咔唑和氰基吡啶的高热稳定性，具有较高的玻璃化转化温度、高的热稳定性和优异的发光性能。
本发明的另一个目的在于提供一种高效、低廉、具有巨大商业价值的一步合成的方法获得一类热激活延迟荧光材料氰基吡啶和咔唑类化合物，其工艺简单，产率高，该材料应用于OLED器件中，其发光层的荧光效率高和稳定性好，进而使OLED器件发光效率和使用寿命都能达到与磷光OLED相媲美。
为实现上述目的，本发明提供一种热激活延迟荧光材料2，3，4，6-CzCNPy，结构如下所示：
将其制备的溶液加工型器件，最大电流效率达39坎特拉每安培，器件最大外量子效率达到12％。
具体实施方式
为了更好地理解本发明，下面通过具体的实施例来具体说明本发明的技术方案。
实施例1：2，3，5，6-四咔唑基-4-氰基吡啶的合成
2，3，5，6-四氟-4-氰基吡啶(0.30g，1.7mmol)，碳酸钾(234g，17mmol)，咔唑(1.42g，8.5mmol)，DMSO 10ml，150℃加热回流12h。冷却至室温倒入200ml水中析出大量固体搅拌0.5h，抽滤得白色固体，柱层析提纯得白色固体1.12g，收率86％。1HNMR(CDCl3，400MHz)：δppm 7.82(t，4H，J＝4.50Hz)，7.75(d，4H，7.50Hz)，7.44(d，4H，J＝780)，7.29(d，4H，3.9Hz)，7.21-7.17(m，8H)，7.13-7.01(m，8H)。
表1为实施例(1)的器件数据，器件结构为：ITO/PEDOT：PSS/mCP or 4CzPy：2，3，5，6-CzCNPy/TMPYPB/LiF/Al。如表1所示制备的器件最大电流效率高达38.9cd/A，最大能量效率17.9m/W。
表1
Claims (4)
1.一种热激活延迟荧光材料氰基吡啶和咔唑化合物，其结构式如下：
2.权利要求1所述的化合物作为绿光延迟荧光发光材料在有机电致发光器件中的应用。
3.根据权利要求2所述的应用，其特征在于：所述有机电致发光器件包括玻璃、附着在玻璃上的导电玻璃衬底层，与导电玻璃衬底层贴合的空穴注入层，与空穴注入层贴合的发光层，与发光层贴合的电子传输层，与电子传输层贴合的阴极层；所述发光层由主体材料与客体材料组成。
4.根据权利要求3所述的应用，其特征在于：发光层的客体材料为权利要求1所述的化合物。
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| JP7083247B2 (ja) * | 2015-05-08 | 2022-06-10 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | 発光材料、発光性薄膜、有機エレクトロルミネッセンス素子、表示装置及び照明装置 |
| JP7081924B2 (ja) * | 2015-05-08 | 2022-06-07 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | 発光材料、発光性薄膜、有機エレクトロルミネッセンス素子、表示装置及び照明装置 |
| CN105400507B (zh) * | 2015-10-15 | 2018-09-18 | 南京邮电大学 | 一类基于热致延迟长寿命荧光有机材料纳米颗粒的制备方法及其时间分辨生物成像应用 |
| US10411211B2 (en) * | 2015-11-10 | 2019-09-10 | Sharp Kabushiki Kaisha | Light-emitting element, method for manufacturing same, and light emission method |
| DE102017109593B4 (de) * | 2017-05-04 | 2018-12-13 | Cynora Gmbh | Organische Moleküle, insbesondere zur Verwendung in optoelektronischen Vorrichtungen |
| WO2019046734A1 (en) * | 2017-09-01 | 2019-03-07 | Kyulux, Inc. | MATERIAL COMPOSITION FOR USE IN ORGANIC ELECTROLUMINESCENT DIODE |
| JP7153363B2 (ja) * | 2017-12-05 | 2022-10-14 | 株式会社Kyulux | 有機発光ダイオードに用いられる組成物 |
| CN108586318B (zh) * | 2018-01-16 | 2020-09-18 | 东南大学 | 一种可溶液加工的热激活延迟荧光材料及其制备方法 |
| CN108329252A (zh) * | 2018-01-16 | 2018-07-27 | 东南大学 | 一种聚集诱导热激活延迟荧光材料及其有机电致发光器件 |
| CN110407810B (zh) * | 2018-04-27 | 2023-11-24 | 北京鼎材科技有限公司 | 一种有机电致发光材料及其应用 |
| CN108864055B (zh) * | 2018-08-03 | 2021-07-30 | 大连理工大学 | 有机电致发光材料及其应用 |
| CN114105868B (zh) * | 2020-09-01 | 2024-03-29 | 江苏三月科技股份有限公司 | 一种以4-氰基吡啶为核心的有机化合物及包含其的有机电致发光器件 |
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| JP5624270B2 (ja) * | 2007-09-18 | 2014-11-12 | ユー・ディー・シー アイルランド リミテッド | 有機電界発光素子 |
| KR20130015370A (ko) * | 2011-08-03 | 2013-02-14 | 엘지디스플레이 주식회사 | 인광 물질 및 이를 이용하는 유기전계발광소자 |
| JP2014135466A (ja) * | 2012-04-09 | 2014-07-24 | Kyushu Univ | 有機発光素子ならびにそれに用いる発光材料および化合物 |
| CN104059090B (zh) * | 2014-06-27 | 2016-07-06 | 南京工业大学 | 一类吡啶和咔啉衍生物的合成方法及其应用 |
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