溶液加工型自主体热活化延迟荧光材料的研究进展

doi:10.6023/A23040119

化学学报 ›› 2023, Vol. 81 ›› Issue (7): 820-835.DOI: 10.6023/A23040119 上一篇下一篇

综述

溶液加工型自主体热活化延迟荧光材料的研究进展

刘振宇, 饶俊峰, 祝守加, 王兵洋, 余帆, 冯全友^*(), 解令海^*()

南京邮电大学信息材料与纳米技术研究院有机电子与信息显示国家重点实验室南京 210023

投稿日期:2023-04-07 发布日期:2023-05-17

作者简介:

刘振宇, 南京邮电大学信息材料与纳米技术研究院/材料科学与工程学院2020级研究生, 导师为冯全友副教授. 主要从事有机发光材料的设计合成及其性能研究.

冯全友, 南京邮电大学化学与生命科学学院副教授、硕士生导师. 2005至2009年就读于西南大学化学与化工学院, 获得学士学位. 2009至2014年就读于复旦大学先进材料实验室, 获得博士学位(导师:周刚教授、王忠胜教授). 随后加入南京邮电大学信息材料与纳米技术研究院/材料科学与工程学院. 2015至2017年在弗吉尼亚理工大学从事博士后研究(导师: Tong Rong教授). 目前主要研究方向为有机/聚合物宽带隙半导体材料及其光电子器件.

解令海, 南京邮电大学信息材料与纳米技术研究院/化学与生命科学学院教授、博士生导师, 国家自然科学基金优秀青年科学基金获得者. 2000年和2003年分别获得东北师范大学学士学位和汕头大学硕士学位. 2003至2006年就读于复旦大学先进材料研究院, 获得博士学位(导师:黄维院士). 长期从事多功能有机半导体材料的设计合成及其在有机发光、有机激光、有机存储和忆阻器等领域的应用研究.

基金资助:
江苏省自然科学基金(BK20190090); 有机电子与信息显示国家重点实验室(GZR2022010020)

Research Progress of Solution-Processed Self-Host Thermally Activated Delayed Fluorescence Materials

Zhenyu Liu, Junfeng Rao, Shoujia Zhu, Bingyang Wang, Fan Yu, Quanyou Feng(), Linghai Xie()

State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, Nanjing 210023

Received:2023-04-07 Published:2023-05-17
Contact: *E-mail: iamqyfeng@njupt.edu.cn; iamlhxie@njupt.edu.cn
Supported by:
Natural Science Foundation of Jiangsu Province(BK20190090); State Key Laboratory of Organic Electronics and Information Displays(GZR2022010020)

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摘要/Abstract

十年来, 作为第三代有机发光二极管(organic light-emitting diodes, OLED)发光材料的热活化延迟荧光(thermally activated delayed fluorescence, TADF)材料备受学术界和产业界的广泛关注. TADF分子由于单重态与三重态之间的能级差较小, 当受到环境热激活时, 三重态激子可以通过反系间窜越转化为单重态, 从理论上讲, 可以实现100%的激子利用率. 这一特性使得OLED器件外量子效率显著提高. 溶液加工法具有成本低、方法简单、材料利用率高、可大面积生产等优势, 是柔性及印刷OLED器件制备工艺的理想候选. 具有良好的电荷传输能力的主体材料能有效降低激子密度和促进能量高效传递. 利用自主体TADF材料制备的溶液加工型器件能有效平衡载流子传输和提升器件性能, 同时在使用过程中可避免相分离, 保持薄膜的均匀性和提高器件的稳定性. 本综述总结了溶液加工型自主体TADF材料的研究进展. 首先介绍了TADF材料的基本原理和研究意义, 强调了溶液加工型自主体TADF材料在显示器件和照明器件等方面的应用潜力. 然后详细讨论了溶液加工型自主体TADF材料的不同分类(小分子、树枝状和聚合物)、材料结构及器件性能等方面的研究进展. 最后, 分别从自主体TADF材料当前的不足、存在的问题和可能解决方案等方面对其发展趋势进行了展望. 本综述旨在为相关领域的研究人员提供参考, 并促进TADF材料的进一步发展和应用.

关键词: 有机发光二极管, 热活化延迟荧光, 溶液加工, 自主体, 非掺杂

Over the past decade, thermally activated delayed fluorescence (TADF) materials have gained widespread attention within both the academic and industrial domains as the third-generation organic light-emitting diode (OLED) emitters. TADF molecules exhibit a small energy gap between the lowest singlet and triplet excited states (ΔE_ST), thereby facilitating the conversion of triplet excitons to singlet states through reverse intersystem crossing (RISC) upon thermal activation. This characteristic presents the theoretical possibility of achieving 100% exciton utilization, thereby substantially enhancing the external quantum efficiency of OLED devices. Solution processing offers several advantages, such as low cost, simple methods, high material utilization, and large-scale production, rendering it an ideal candidate for the fabrication of flexible and printable OLED devices. The host material with excellent charge transfer capabilities can effectively reduce exciton density and facilitate efficient energy transfer. Consequently, solution-processed devices constructed using self-host TADF materials can effectively balance charge carrier transport and avoid phase separation, thereby maintaining film uniformity, enhancing device performance and improving device stability. This review provides a comprehensive summary of the advancements made in the field of solution-processed self-host TADF materials. First, the basic principles and research significance of TADF materials are introduced, highlighting the potential applications of solution-processed self-host TADF materials in display and lighting devices. Subsequently, an overview of the current research progress on various classifications of solution-processed self-host TADF materials, including small molecules, dendrimers, and polymers are presented. Special emphasis is placed on elucidating the material structures and their performance within devices. Finally, a future outlook is provided regarding the development trend of self-host TADF materials, including their current deficiencies, existing issues, and potential solutions. The review aims to serve as a valuable reference for researchers in related fields, while simultaneously fostering further advancement and application of TADF materials.

Key words: organic light-emitting diode, thermally activated delayed fluorescence, solution-processed, self-host, non-doped

引用此文

刘振宇, 饶俊峰, 祝守加, 王兵洋, 余帆, 冯全友, 解令海. 溶液加工型自主体热活化延迟荧光材料的研究进展[J]. 化学学报, 2023, 81(7): 820-835.

Zhenyu Liu, Junfeng Rao, Shoujia Zhu, Bingyang Wang, Fan Yu, Quanyou Feng, Linghai Xie. Research Progress of Solution-Processed Self-Host Thermally Activated Delayed Fluorescence Materials[J]. Acta Chimica Sinica, 2023, 81(7): 820-835.

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Emitter	T_g/T_d /℃	λ_PL/nm	PLQY^d/% (Sol./film)	ΔE_ST/eV	λ_EL/nm	CIE	EQE/%	Ref.
S1	—/419	650^a/634^c	—	0.16^b,f	652	(0.63, 0.32)	2.3	[68]
S2	—/394	558^a/555^c	—	—	540	(0.38, 0.52)	0.3	[68]
S3	171/450	498^a/526^b	80^e/100^e	0.4^a,f	520	(0.30, 0.58)	4.9	[70]
S4	211/516	473^a/495^b	11^e/46^e	0.39^a,f	520	(0.31, 0.54)	8.3	[70]
S5	218/505	504^a/522^b	36^e/89^e	0.166^b,f	524	(0.33, 0.54)	13.4	[71]
S6	72/309	518^b	—	0.1^b,f	522	(0.28, 0.59)	8.15	[72]
S7	158/435	514^a	—/92.3	0.02^a,f	494	(0.21, 0.43)	23.0	[54]
S8	144/459	576^a/530^b	3.9/69	0.024^b,f	548	(0.39, 0.57)	22.6	[73]
S9	155/537	575^a/532^b	3/71.6	0.02^b,f	546	(0.39, 0.57)	21.4	[73]
S10	136/469	575^a/529^b	3.1/66	0.024^b,f	542	(0.39, 0.57)	22.1	[73]
S11	141/452	574^a/530^b	2.8/71.2	0.016^b,f	542	(0.38, 0.57)	21.8	[73]
S12	173/528	537^b	—/40	0.08^b,f	520	(0.32, 0.56)	13.9	[74]
S13	161/484	537^b	—/47	0.05^b,f	520	(0.32, 0.56)	14.7	[74]
S14	174/507	548^b	—/55	0.03^b,f	523	(0.34, 0.56)	17.1	[74]
S15	—/507	548^b	—/56	0.03^b,f	521	(0.34, 0.56)	18.1	[74]
D1	—/388	667^a/715^b	6/—	0.17^a,f	728	(0.70, 0.29)	0.064	[76]
D2	—/427	667^a/708^b	8/—	0.16^a,f	715	(0.69, 0.30)	0.254	[76]
D3	—/400	667^a	—/10	0.17^a,f	698	(0.67, 0.31)	0.62	[77]
D4	—/388	594^a/545^b	—/56	0.17^a,f	550	(0.41, 0.54)	5.5	[79]
D5	—/427	591^a/541^b	—/71	0.20^a,f	546	(0.39, 0.56)	11.8	[79]
D6	96/382	535^a/490^b	—/58	0.20^a,f	520	(0.24, 0.51)	6.5	[80]
D7	128/407	535^a/487^b	—/76	0.20^a,f	520	(0.24, 0.51)	10.1	[80]
D8	—/—	517^a/520^b	—/69.2	0.079^b,f	520	(0.32, 0.57)	9.5	[81]
D9	—/—	495^a/494^b	—/56.4	0.134^b,f	496	(0.22, 0.43)	8.1	[81]
D10	128/402	—/—	88/52	0.17 ^f	510	(0.25, 0.52)	15.5	[82]
D11	135/419	527^a/548^b	—/—	0.09^a,f	552	(0.46, 0.52)	0.5	[83]
D12	141/382	527^a/548^b	—/—	0.08^a,f	548	(0.42, 0.55)	16.5	[83]
D13	80/380	475^a/440^b	—/—	0.21^a,f	464	(0.16, 0.19)	2.6	[84]
D14	113/410	475^a/458^b	—/—	0.11^a,f	480	(0.18, 0.27)	6.2	[84]
D15	145/450	490^a/460^b	—/61	0.23^a,f	480	(0.18, 0.30)	7.3	[85]
D16	—/592	473^a	94/52	0.03^b,f	470	(0.25, 0.49)	2.4	[87]
D17	—/620	473^a	100/31	0.06^b,f	508	(0.27 0.49)	3.4	[87]
D18	—/633	473^a	94/8.5	0.06^b,f	480	(0.23, 0.37)	1.5	[87]
D19	—	—	94/52	0.13^b,f	—	—	6.0	[88]
D20	—	—	92/40	0.07^b,f	—	—	9.4	[88]
D21	—	—	96/45	0.07^b,f	—	—	9.5	[88]
D22	—	—	95/49	0.08^b,f	—	—	8.2	[88]
D23	—	461^a/493^b	23.6/33.4	0.12^b,f	500	(0.25, 0.44)	5.7	[89]
D24	—	461^a/500^b	14.7/21.1	0.10^b,f	516	(0.31, 0.50)	2.9	[89]
D25	—	473^a/501^b	47/74	0.08^b,f	500	(0.27, 0.52)	17	[90]
D26	—	473^a/501^b	48/34	0.08^b,f	500	(0.28, 0.48)	9	[90]
D27	—	497^a/539^b	74/17	0.11^b,f	550	(0.44, 0.51)	6.4	[90]
D28	—	464^a/507^b	32/41	0.14^b,f	500	(0.30, 0.48)	8.8	[90]
D29	283/471	520^b	—/77	0.11^b,f	552	(0.40, 0.54)	13.8	[91]
D30	289/507	499^b	—/75	0.15^b,f	522	(0.32, 0.51)	5.2	[91]
D31	272/459	492^b	—/67.5	0.09 ^f	492	(0.22, 0.44)	12.2	[92]
D32	274/479	464^b	—/48.2	0.20^f	464	(0.18, 0.27)	2.2	[92]
D33	242/372	426^a/438^b	64/58	0.25^b,f	426	(0.15, 0.12)	—	[86]
D34	325/425	439^a/451^b	52/22	0.17^b,f	439	(0.19, 0.15)	—	[86]
D33	207/394	490^b	—/47	0.10^a,f	510	(0.28, 0.53)	7.65	[96]
D35	213/427	400^b	—/33	0.22^a,f	410	(0.26,0.31)	2	[96]
P1	122/338	491^a/470^b	27.5/—	—	478	(0.19, 0.25)	1.2	[100]
P2	122/320	491^a/479^b	27.2/—	—	492	(0.21, 0.32)	1.1	[100]
P3	129/336	491^a/491^b	33.6/—	—	498	(0.22, 0.37)	4.0	[100]
P4	126/342	491^a/494^b	33.7/—	—	506	(0.24, 0.43)	4.3	[1000]
P5	—/—	507^a/497^b	50/39	—	—	—	—	[101]
P6	—/—	511^a/500^b	67/74	—	496	(0.29, 0.47)	2.8	[101]
P7	—/—	512^a/506^b	66/70	—	—	—	—	[101]
P8	—/—	513^a/509^b	60/59	0.02^b,f	—	—	—	[101]
P9	—/456	596^a/523^b	—/68	—	540	(0.37, 0.54)	5.5	[102]
P10	—/456	596^a/530^b	—/71	—	547	(0.40, 0.54)	7.0	[102]
P11	—/454	596^a/531^b	—/70	0.06^b,f	550	(0.41, 0.54)	7.0	[102]
P12	—/457	596^a/533^b	—/64	—	552	(0.42, 0.54)	6.9	[102]
P13	142/292	527^b	35/—	0.09^b,f	539	(0.33, 0.51)	13.0	[103]
P14	146/297	533^b	48/—	0.06^b,f	543	(0.34, 0.51)	13.9	[103]
P15	148/318	540^b	57/—	0.06^b,f	546	(0.35, 0.53)	15.3	[103]
P16	149/318	544^b	47/—	0.05^b,f	548	(0.38, 0.54)	8.3	[103]
P17	199/388	535^b	18/—	0.07^a,f	548	(0.38, 0.53)	0.6	[104]
P18	218/389	538^b	25/—	0.06^a,f	552	(0.40, 0.55)	1.2	[104]
P19	226/389	543^b	22/—	0.05^a,f	556	(0.42, 0.54)	1.0	[104]
P20	176/375	538^b	31/—	0.13^b,f	536	(0.36, 0.49)	3.5	[104]
P21	180/378	541^b	52/—	0.11^a,f	540	(0.36, 0.50)	5.2	[104]
P22	181/379	542^b	39/—	0.09^a,f	544	(0.37, 0.51)	4.1	[104]
P23	93/441	495^a/496^b	—	0.02^b,f	498	(0.23, 0.39)	9.0	[105]

Emitter	T_g/T_d /℃	λ_PL/nm	PLQY^d/% (Sol./film)	ΔE_ST/eV	λ_EL/nm	CIE	EQE/%	Ref.
S1	—/419	650^a/634^c	—	0.16^b,f	652	(0.63, 0.32)	2.3	[68]
S2	—/394	558^a/555^c	—	—	540	(0.38, 0.52)	0.3	[68]
S3	171/450	498^a/526^b	80^e/100^e	0.4^a,f	520	(0.30, 0.58)	4.9	[70]
S4	211/516	473^a/495^b	11^e/46^e	0.39^a,f	520	(0.31, 0.54)	8.3	[70]
S5	218/505	504^a/522^b	36^e/89^e	0.166^b,f	524	(0.33, 0.54)	13.4	[71]
S6	72/309	518^b	—	0.1^b,f	522	(0.28, 0.59)	8.15	[72]
S7	158/435	514^a	—/92.3	0.02^a,f	494	(0.21, 0.43)	23.0	[54]
S8	144/459	576^a/530^b	3.9/69	0.024^b,f	548	(0.39, 0.57)	22.6	[73]
S9	155/537	575^a/532^b	3/71.6	0.02^b,f	546	(0.39, 0.57)	21.4	[73]
S10	136/469	575^a/529^b	3.1/66	0.024^b,f	542	(0.39, 0.57)	22.1	[73]
S11	141/452	574^a/530^b	2.8/71.2	0.016^b,f	542	(0.38, 0.57)	21.8	[73]
S12	173/528	537^b	—/40	0.08^b,f	520	(0.32, 0.56)	13.9	[74]
S13	161/484	537^b	—/47	0.05^b,f	520	(0.32, 0.56)	14.7	[74]
S14	174/507	548^b	—/55	0.03^b,f	523	(0.34, 0.56)	17.1	[74]
S15	—/507	548^b	—/56	0.03^b,f	521	(0.34, 0.56)	18.1	[74]
D1	—/388	667^a/715^b	6/—	0.17^a,f	728	(0.70, 0.29)	0.064	[76]
D2	—/427	667^a/708^b	8/—	0.16^a,f	715	(0.69, 0.30)	0.254	[76]
D3	—/400	667^a	—/10	0.17^a,f	698	(0.67, 0.31)	0.62	[77]
D4	—/388	594^a/545^b	—/56	0.17^a,f	550	(0.41, 0.54)	5.5	[79]
D5	—/427	591^a/541^b	—/71	0.20^a,f	546	(0.39, 0.56)	11.8	[79]
D6	96/382	535^a/490^b	—/58	0.20^a,f	520	(0.24, 0.51)	6.5	[80]
D7	128/407	535^a/487^b	—/76	0.20^a,f	520	(0.24, 0.51)	10.1	[80]
D8	—/—	517^a/520^b	—/69.2	0.079^b,f	520	(0.32, 0.57)	9.5	[81]
D9	—/—	495^a/494^b	—/56.4	0.134^b,f	496	(0.22, 0.43)	8.1	[81]
D10	128/402	—/—	88/52	0.17 ^f	510	(0.25, 0.52)	15.5	[82]
D11	135/419	527^a/548^b	—/—	0.09^a,f	552	(0.46, 0.52)	0.5	[83]
D12	141/382	527^a/548^b	—/—	0.08^a,f	548	(0.42, 0.55)	16.5	[83]
D13	80/380	475^a/440^b	—/—	0.21^a,f	464	(0.16, 0.19)	2.6	[84]
D14	113/410	475^a/458^b	—/—	0.11^a,f	480	(0.18, 0.27)	6.2	[84]
D15	145/450	490^a/460^b	—/61	0.23^a,f	480	(0.18, 0.30)	7.3	[85]
D16	—/592	473^a	94/52	0.03^b,f	470	(0.25, 0.49)	2.4	[87]
D17	—/620	473^a	100/31	0.06^b,f	508	(0.27 0.49)	3.4	[87]
D18	—/633	473^a	94/8.5	0.06^b,f	480	(0.23, 0.37)	1.5	[87]
D19	—	—	94/52	0.13^b,f	—	—	6.0	[88]
D20	—	—	92/40	0.07^b,f	—	—	9.4	[88]
D21	—	—	96/45	0.07^b,f	—	—	9.5	[88]
D22	—	—	95/49	0.08^b,f	—	—	8.2	[88]
D23	—	461^a/493^b	23.6/33.4	0.12^b,f	500	(0.25, 0.44)	5.7	[89]
D24	—	461^a/500^b	14.7/21.1	0.10^b,f	516	(0.31, 0.50)	2.9	[89]
D25	—	473^a/501^b	47/74	0.08^b,f	500	(0.27, 0.52)	17	[90]
D26	—	473^a/501^b	48/34	0.08^b,f	500	(0.28, 0.48)	9	[90]
D27	—	497^a/539^b	74/17	0.11^b,f	550	(0.44, 0.51)	6.4	[90]
D28	—	464^a/507^b	32/41	0.14^b,f	500	(0.30, 0.48)	8.8	[90]
D29	283/471	520^b	—/77	0.11^b,f	552	(0.40, 0.54)	13.8	[91]
D30	289/507	499^b	—/75	0.15^b,f	522	(0.32, 0.51)	5.2	[91]
D31	272/459	492^b	—/67.5	0.09 ^f	492	(0.22, 0.44)	12.2	[92]
D32	274/479	464^b	—/48.2	0.20^f	464	(0.18, 0.27)	2.2	[92]
D33	242/372	426^a/438^b	64/58	0.25^b,f	426	(0.15, 0.12)	—	[86]
D34	325/425	439^a/451^b	52/22	0.17^b,f	439	(0.19, 0.15)	—	[86]
D33	207/394	490^b	—/47	0.10^a,f	510	(0.28, 0.53)	7.65	[96]
D35	213/427	400^b	—/33	0.22^a,f	410	(0.26,0.31)	2	[96]
P1	122/338	491^a/470^b	27.5/—	—	478	(0.19, 0.25)	1.2	[100]
P2	122/320	491^a/479^b	27.2/—	—	492	(0.21, 0.32)	1.1	[100]
P3	129/336	491^a/491^b	33.6/—	—	498	(0.22, 0.37)	4.0	[100]
P4	126/342	491^a/494^b	33.7/—	—	506	(0.24, 0.43)	4.3	[1000]
P5	—/—	507^a/497^b	50/39	—	—	—	—	[101]
P6	—/—	511^a/500^b	67/74	—	496	(0.29, 0.47)	2.8	[101]
P7	—/—	512^a/506^b	66/70	—	—	—	—	[101]
P8	—/—	513^a/509^b	60/59	0.02^b,f	—	—	—	[101]
P9	—/456	596^a/523^b	—/68	—	540	(0.37, 0.54)	5.5	[102]
P10	—/456	596^a/530^b	—/71	—	547	(0.40, 0.54)	7.0	[102]
P11	—/454	596^a/531^b	—/70	0.06^b,f	550	(0.41, 0.54)	7.0	[102]
P12	—/457	596^a/533^b	—/64	—	552	(0.42, 0.54)	6.9	[102]
P13	142/292	527^b	35/—	0.09^b,f	539	(0.33, 0.51)	13.0	[103]
P14	146/297	533^b	48/—	0.06^b,f	543	(0.34, 0.51)	13.9	[103]
P15	148/318	540^b	57/—	0.06^b,f	546	(0.35, 0.53)	15.3	[103]
P16	149/318	544^b	47/—	0.05^b,f	548	(0.38, 0.54)	8.3	[103]
P17	199/388	535^b	18/—	0.07^a,f	548	(0.38, 0.53)	0.6	[104]
P18	218/389	538^b	25/—	0.06^a,f	552	(0.40, 0.55)	1.2	[104]
P19	226/389	543^b	22/—	0.05^a,f	556	(0.42, 0.54)	1.0	[104]
P20	176/375	538^b	31/—	0.13^b,f	536	(0.36, 0.49)	3.5	[104]
P21	180/378	541^b	52/—	0.11^a,f	540	(0.36, 0.50)	5.2	[104]
P22	181/379	542^b	39/—	0.09^a,f	544	(0.37, 0.51)	4.1	[104]
P23	93/441	495^a/496^b	—	0.02^b,f	498	(0.23, 0.39)	9.0	[105]

溶液加工型自主体热活化延迟荧光材料的研究进展

Research Progress of Solution-Processed Self-Host Thermally Activated Delayed Fluorescence Materials

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