高结晶性小分子给体材料应用于全小分子有机太阳能电池中的研究进展

doi:10.6023/A20090450

化学学报 ›› 2021, Vol. 79 ›› Issue (3): 284-302.DOI: 10.6023/A20090450 上一篇下一篇

综述

高结晶性小分子给体材料应用于全小分子有机太阳能电池中的研究进展

吕敏^a^,^b, 周瑞敏^a^,^b, 吕琨^a^,^b^,^*(), 魏志祥^a^,^b

a 中国科学院纳米系统与多级次制造重点实验室中国科学院纳米科学卓越中心国家纳米科学中心北京 100190
b 中国科学院大学北京 100049

投稿日期:2020-09-27 发布日期:2020-12-01
通讯作者: 吕琨

作者简介:

吕敏, 硕士研究生. 2019年6月于青岛科技大学材料科学与工程学院新能源材料与器件专业取得学士学位, 同年9月进入国家纳米科学中心魏志祥研究员课题组开展硕士研究工作. 目前其主要的研究方向为小分子给体材料的设计与合成, 主要研究高结晶性小分子给体材料应用于非富勒烯全小分子有机太阳能电池中对形貌调控的影响.

周瑞敏, 2015年本科毕业于河南大学化学实验班, 自2015年9月进入国家纳米科学中心(中国科学院大学中丹学院)硕博连读, 研究方向主要是可溶性有机光伏小分子给体的设计合成与器件制备研究. 目前发表的文章包括Nature Communications一篇, Advanced Functional Materials一篇等.

吕琨, 国家纳米科学中心研究员, 博士生导师. 2004年7月毕业于山东大学化学与化工学院, 获得学士学位; 2009年12月于中国科学院化学研究所获得博士学位; 2010年1月至今, 任职国家纳米科学中心研究员. 研究重点是用于光伏器件的聚合物和小分子半导体材料的合成及其在大面积柔性器件中的应用. 基于以上研究, 发表了90多篇论文, 被引用超过2000次; 并且获得了中国化学会青年化学奖、北京市科技新星计划、中国科学院青年创新促进会优秀会员和国家优秀青年科学基金等基金支持.

魏志祥, 国家纳米科学中心研究员, 博士生导师. 1997和2000年分别在西安交通大学获得学士和硕士学位, 2003年中国科学院化学研究所获得博士学位. 之后分别在德国马普胶体界面研究所和多伦多大学从事博士后研究. 2006年加入国家纳米中心工作. 主要研究领域为有机光电功能纳米材料与柔性器件, 研究通过自组装方法制备结构和性能可控的有机光电功能纳米材料, 并探索其在手性传感器件、太阳能电池和储能器件等柔性器件中的应用.

* E-mail: lvk@nanoctr.cn

基金资助:
项目受国家自然科学基金(21822503); 项目受国家自然科学基金(51973043); 项目受国家自然科学基金(21534003); 项目受国家自然科学基金(21721002); 青年创新促进协会基金资助.

Research Progress of Small Molecule Donors with High Crystallinity in All Small Molecule Organic Solar Cells

Min Lv^a^,^b, Ruimin Zhou^a^,^b, Kun Lu^a^,^b^,^*(), Zhixiang Wei^a^,^b

a CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China
b University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-09-27 Published:2020-12-01
Contact: Kun Lu
Supported by:
National Natural Science Foundation of China(21822503); National Natural Science Foundation of China(51973043); National Natural Science Foundation of China(21534003); National Natural Science Foundation of China(21721002); Youth Innovation Promotion Association.

文章分享

摘要/Abstract

随着新型小分子给体材料和非富勒烯小分子受体材料的开发和应用, 非富勒烯全小分子有机太阳能电池(NF-ASM OSCs)的光电转换效率已经突破15%, 并逐渐接近聚合物太阳能电池的效率. 相比于聚合物电子给体材料, 小分子电子给体材料拥有其独特的优势, 例如合成批次性差异小、分子量明确和易于提纯等; 但是, 对小分子给体材料的结晶性难于精确调控, 使获得合适的纳米级结构的混合膜仍然是一个挑战. 本综述以给体小分子中心共轭单元的扩展为主线, 从分子设计的角度汇总了近年来对苯并二噻吩、萘并二噻吩和二噻并苯并二噻吩类小分子给体材料的结晶性研究, 并为进一步改善电池活性层形貌和获得更高的光伏性能提供了未来发展的建议.

关键词: 全小分子有机太阳能电池, 小分子电子给体材料, 中心共轭单元, 分子设计, 结晶性

In the past few decades, organic solar cells (OSCs) have been extensively studied due to their advantages of semitransparency, light-weight and flexibility, which are considered to be an important renewable energy source in the future. Recently, bulk heterojunction all-small molecule organic solar cells (BHJ ASM-OSCs) composed of p-type small molecule donors and n-type non-fullerene acceptors as the active layers have achieved remarkable development and the power conversion efficiencies (PCEs) have exceeded 15%. The advantages of non-fullerene acceptors over fullerene competitors are their easily tunable energy levels, better absorption properties and proper molecular designs, which allow ASM-OSCs to achieve significantly higher open-circuit voltages, higher photocurrents and superior stability, thus extending the device lifetime of OSCs. Compared with p-type polymer donors, p-type small molecule donors have unique advantages, such as well-defined molecular structures, easy purification and low batch-to-batch variations. Although ASM-OSCs are expected to take advantages of non-fullerene acceptors and small molecule donors simultaneously, in consequence of inappropriate crystallinity and nano-scale bi-continuous interpenetrating networks in blended films resulting from similar acceptor-donor-acceptor (A-D-A) structures and physicochemical properties between small molecule donors and non-fullerene acceptors, the PCEs of current state-of-the-art ASM-OSCs are still much lower than that of polymer-based OSCs. In this review, based on the expansion of the central conjugated units of small molecular donors, we summarized the crystallinity of benzodithiophene (BDT), naphthodithiophene (NDT) and dithienobenzodithiophene (DTBDT) donors from the perspective of molecular design and provided suggestions for further molecular design and morphology improvement.

Key words: all small molecule organic solar cell, small molecule donor, central conjugated unit, molecular design, crystallinity

引用此文

吕敏, 周瑞敏, 吕琨, 魏志祥. 高结晶性小分子给体材料应用于全小分子有机太阳能电池中的研究进展[J]. 化学学报, 2021, 79(3): 284-302.

Min Lv, Ruimin Zhou, Kun Lu, Zhixiang Wei. Research Progress of Small Molecule Donors with High Crystallinity in All Small Molecule Organic Solar Cells[J]. Acta Chimica Sinica, 2021, 79(3): 284-302.

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图/表 14

图1. 苯并二噻吩类小分子电子给体材料的化学结构(1~25)

Figure 1. Chemical structures of BDT-based small molecule electron donors (1~25)

图2. 苯并二噻吩类小分子电子给体材料的化学结构(26~45)

Figure 2. Chemical structures of BDT-based small molecule electron donors (26~45)

Donor	HOMO/LUMO (eV)	E_g^a/eV	Acceptor	μ_h×10^–4/ (cm²·V^–1·s^–1)	V_oc/V	J_sc/(mA·cm^–2)	FF/%	PCE/%	Reference
1	-5.31/-3.03	1.87	IDIC	0.77	0.977	15.21	65.46	9.73	[47]
2	-5.28/-3.01	1.87	IDIC	0.79	0.955	10.51	54.89	5.51	[47]
3	-5.48/-3.56	1.90	IDIC	3.46	0.98	14.22	65	9.06	[49]
4	-5.50/-3.56	1.90	IDIC	0.00374	0.99	0.57	27	0.15	[49]
5	-5.33/-3.18	1.82	IDIC	1.48	0.98	15.92	71.15	11.10	[48]
6	-5.39/-3.35	1.86	F-2Cl	2.10	0.95	15.72	62.8	9.37	[50]
7	-5.40/-3.24	1.83	F-2Cl	2.80	1.00	16.82	62.6	10.45	[50]
8	-5.31/-3.36	1.79	F-2Cl	1.37	0.88	14.23	55.6	6.95	[50]
9	-5.29/-3.32	1.83	F-2Cl	1.13	0.99	9.36	52.3	4.85	[50]
10	—	—	BO-4Cl	23	0.83	25.27	73	15.3	[51]
11	—	—	BO-4Cl	14	0.83	18.60	72	11.2	[51]
12	-5.24/-3.41	1.57	IDIC	0.872	0.90	13.98	65.20	8.23	[52]
13	-5.19/-3.37	1.57	IDIC	0.726	0.90	12.05	57.20	6.21	[52]
14	-5.37/-2.81	1.88	Y6	3.87	0.866	23.25	69.9	14.07	[53]
15	-5.32/-2.81	1.85	Y6	3.67	0.825	23.23	67.7	12.94	[53]
16	-5.25/-2.78	1.85	Y6	4.12	0.805	23.59	67.0	12.72	[53]
17	-5.39/-3.38	2.19	Y6	5.18	0.854	21.55	72.35	13.34	[54]
18	-5.37/-3.37	2.19	Y6	4.17	0.870	21.21	61.35	11.33	[54]
19	-5.43/-3.39	1.93	IDIC-4F	1.18	0.939	17.30	63.2	10.30	[55]
20	-5.46/-3.47	1.94	IDIC-4F	4.61	0.943	18.30	70.2	12.10	[55]
21	-5.64/-3.61	1.99	F-2Cl	0.856	1.07	13.46	53.20	7.66	[56]
22	-5.34/-3.53	1.78	Y6	3.01	0.85	22.25	56.4	10.67	[57]
23	-5.46/-3.70	1.78	Y6	2.72	0.86	24.17	65.5	13.61	[57]
24	-5.56/-3.35	1.90	IDIC	3.48	1.06	4.75	29.31	1.56	[59]
25	-5.54/-3.31	1.90	IDIC	46.7	1.04	10.10	58.84	6.17	[59]
26	-5.30/-3.41	1.79	IDIC-4F	4.29	0.91	11.04	41.00	10.69	[60]
27	-5.31/-3.43	1.82	IDIC-4F	6.94	0.89	11.46	45.00	11.15	[60]
28	-5.38/-3.63	1.81	IDIC	2.49	0.895	13.00	65.58	7.62	[61]
29	-5.39/-3.59	1.89	IDIC	4.26	0.942	15.38	71.15	10.29	[61]
30	-5.59/-3.34	1.87	IDIC-4Cl	0.417	0.564	4.90	33.90	0.90	[62]
31	-5.58/-3.39	1.82	IDIC-4Cl	3.83	0.865	20.10	71.30	12.40	[62]
32	-5.55/-3.37	1.84	IDIC-4Cl	1.58	0.870	14.20	67.0	8.25	[62]
33	-5.51/-3.34	—	IT-4F	0.327	0.893	16.66	64.00	9.52	[63]
34	-5.50/-3.32	—	IT-4F	1.74	0.909	18.27	68.00	11.24	[63]
35	-5.50/-3.32	—	IT-4F	0.555	0.929	17.92	63.00	10.52	[63]
36	-5.52/-3.33	—	IT-4F	0.314	0.928	16.15	61.00	9.14	[63]
37	-5.05/-3.30	1.75	IDIC	6.45	0.88	15.37	66.56	9.01	[64]
38	-5.05/-3.30	1.75	IDIC	5.44	0.87	14.85	64.88	8.36	[64]
39	-5.40/-3.61	1.79	IDIC	2.40	1.01	14.60	53.00	7.80	[66]
40	-5.25/-3.55	1.77	IDIC	3.50	0.97	15.15	62.50	9.20	[66]
Donor	HOMO/LUMO (eV)	E_g^a/eV	Acceptor	μ_h×10^–4/ (cm²·V^–1·s^–1)	V_oc/V	J_sc/(mA·cm^–2)	FF/%	PCE/%	Reference
41	-5.40/-3.27	1.79	Y6	16.9	0.84	21.1	68.40	12.30	[67]
42	-5.36/-3.24	1.76	Y6	16.8	0.83	22.3	56.20	10.8	[67]
43	-5.39/-3.38	—	Y6	3.30	0.854	21.55	72.35	13.34	[68]
44	-5.40/-3.40	—	Y6	3.93	0.853	22.38	72.27	13.80	[68]
44	-5.40/-3.40	—	N3	—	0.840	23.81	70.22	14.09	[68]
45	-5.02/-3.27	1.72	O-IDTBR	2.21	1.15	11.06	50.00	6.36	[108]
23	-5.42/-3.70	—	Y6	9.78	0.838	23.75	77.11	15.34	[15]

Donor	HOMO/LUMO (eV)	E_g^a/eV	Acceptor	μ_h×10^–4/ (cm²·V^–1·s^–1)	V_oc/V	J_sc/(mA·cm^–2)	FF/%	PCE/%	Reference
1	-5.31/-3.03	1.87	IDIC	0.77	0.977	15.21	65.46	9.73	[47]
2	-5.28/-3.01	1.87	IDIC	0.79	0.955	10.51	54.89	5.51	[47]
3	-5.48/-3.56	1.90	IDIC	3.46	0.98	14.22	65	9.06	[49]
4	-5.50/-3.56	1.90	IDIC	0.00374	0.99	0.57	27	0.15	[49]
5	-5.33/-3.18	1.82	IDIC	1.48	0.98	15.92	71.15	11.10	[48]
6	-5.39/-3.35	1.86	F-2Cl	2.10	0.95	15.72	62.8	9.37	[50]
7	-5.40/-3.24	1.83	F-2Cl	2.80	1.00	16.82	62.6	10.45	[50]
8	-5.31/-3.36	1.79	F-2Cl	1.37	0.88	14.23	55.6	6.95	[50]
9	-5.29/-3.32	1.83	F-2Cl	1.13	0.99	9.36	52.3	4.85	[50]
10	—	—	BO-4Cl	23	0.83	25.27	73	15.3	[51]
11	—	—	BO-4Cl	14	0.83	18.60	72	11.2	[51]
12	-5.24/-3.41	1.57	IDIC	0.872	0.90	13.98	65.20	8.23	[52]
13	-5.19/-3.37	1.57	IDIC	0.726	0.90	12.05	57.20	6.21	[52]
14	-5.37/-2.81	1.88	Y6	3.87	0.866	23.25	69.9	14.07	[53]
15	-5.32/-2.81	1.85	Y6	3.67	0.825	23.23	67.7	12.94	[53]
16	-5.25/-2.78	1.85	Y6	4.12	0.805	23.59	67.0	12.72	[53]
17	-5.39/-3.38	2.19	Y6	5.18	0.854	21.55	72.35	13.34	[54]
18	-5.37/-3.37	2.19	Y6	4.17	0.870	21.21	61.35	11.33	[54]
19	-5.43/-3.39	1.93	IDIC-4F	1.18	0.939	17.30	63.2	10.30	[55]
20	-5.46/-3.47	1.94	IDIC-4F	4.61	0.943	18.30	70.2	12.10	[55]
21	-5.64/-3.61	1.99	F-2Cl	0.856	1.07	13.46	53.20	7.66	[56]
22	-5.34/-3.53	1.78	Y6	3.01	0.85	22.25	56.4	10.67	[57]
23	-5.46/-3.70	1.78	Y6	2.72	0.86	24.17	65.5	13.61	[57]
24	-5.56/-3.35	1.90	IDIC	3.48	1.06	4.75	29.31	1.56	[59]
25	-5.54/-3.31	1.90	IDIC	46.7	1.04	10.10	58.84	6.17	[59]
26	-5.30/-3.41	1.79	IDIC-4F	4.29	0.91	11.04	41.00	10.69	[60]
27	-5.31/-3.43	1.82	IDIC-4F	6.94	0.89	11.46	45.00	11.15	[60]
28	-5.38/-3.63	1.81	IDIC	2.49	0.895	13.00	65.58	7.62	[61]
29	-5.39/-3.59	1.89	IDIC	4.26	0.942	15.38	71.15	10.29	[61]
30	-5.59/-3.34	1.87	IDIC-4Cl	0.417	0.564	4.90	33.90	0.90	[62]
31	-5.58/-3.39	1.82	IDIC-4Cl	3.83	0.865	20.10	71.30	12.40	[62]
32	-5.55/-3.37	1.84	IDIC-4Cl	1.58	0.870	14.20	67.0	8.25	[62]
33	-5.51/-3.34	—	IT-4F	0.327	0.893	16.66	64.00	9.52	[63]
34	-5.50/-3.32	—	IT-4F	1.74	0.909	18.27	68.00	11.24	[63]
35	-5.50/-3.32	—	IT-4F	0.555	0.929	17.92	63.00	10.52	[63]
36	-5.52/-3.33	—	IT-4F	0.314	0.928	16.15	61.00	9.14	[63]
37	-5.05/-3.30	1.75	IDIC	6.45	0.88	15.37	66.56	9.01	[64]
38	-5.05/-3.30	1.75	IDIC	5.44	0.87	14.85	64.88	8.36	[64]
39	-5.40/-3.61	1.79	IDIC	2.40	1.01	14.60	53.00	7.80	[66]
40	-5.25/-3.55	1.77	IDIC	3.50	0.97	15.15	62.50	9.20	[66]
Donor	HOMO/LUMO (eV)	E_g^a/eV	Acceptor	μ_h×10^–4/ (cm²·V^–1·s^–1)	V_oc/V	J_sc/(mA·cm^–2)	FF/%	PCE/%	Reference
41	-5.40/-3.27	1.79	Y6	16.9	0.84	21.1	68.40	12.30	[67]
42	-5.36/-3.24	1.76	Y6	16.8	0.83	22.3	56.20	10.8	[67]
43	-5.39/-3.38	—	Y6	3.30	0.854	21.55	72.35	13.34	[68]
44	-5.40/-3.40	—	Y6	3.93	0.853	22.38	72.27	13.80	[68]
44	-5.40/-3.40	—	N3	—	0.840	23.81	70.22	14.09	[68]
45	-5.02/-3.27	1.72	O-IDTBR	2.21	1.15	11.06	50.00	6.36	[108]
23	-5.42/-3.70	—	Y6	9.78	0.838	23.75	77.11	15.34	[15]

表1. 苯并二噻吩类小分子电子给体材料在ASM-OSCs中的光伏性能

Table 1. Photovoltaic properties of BDT-based small molecule electron donors in ASM-OSCs

表1. 苯并二噻吩类小分子电子给体材料在ASM-OSCs中的光伏性能

Table 1. Photovoltaic properties of BDT-based small molecule electron donors in ASM-OSCs

图3. A: (a) GIWAXS切线图; GIWAXS图像 (b) 1 (H11), (c) IDIC, (d) 1 (H11):IDIC (无后处理)和(e) 1 (H11):IDIC (热退火); B: (a) GIWAXS切线图; GIWAXS图像 (b) 2 (H12), (c) IDIC, (d) 2 (H12):IDIC (无后处理)和(e) 2 (H12):IDIC (热退火). 版权2017, 美国化学学会[47].

Figure 3. A: (a) Line cuts of the GIWAXS images; the GIWAXS images of (b) 1 (H11), (c) IDIC, (d) 1 (H11):IDIC (as-cast) and (e) 1 (H11):IDIC (thermal annealed); B: (a) Line cuts of the GIWAXS images; the GIWAXS images of (b) 2 (H12), (c) IDIC, (d) 2 (H12):IDIC (as-cast) and (e) 2 (H12):IDIC (thermal annealed). Copyright 2017, American Chemical Society[47].

图4. A: (a~d) 给体30 (BSCl-C1), 31 (BSCl-C2)和32 (BSCl-C3)以及受体IDIC-4Cl单组分膜的2D GIWAXS图像; (e~g) 改善条件下混合膜的2D GIWAXS图像; (h) 改善条件下30, 31, 32和IDIC-4Cl单组分及其混合膜的1D GIWAXS切线图; B: (a~c) 基于不同给体30, 31和32混合膜的TEM图像; (d~f) 对应的AFM高度图; 版权2020, 美国化学学会[62].

Figure 4. A: (a~d) 2D GIWAXS patterns of donors 30 (BSCl-C1), 31 (BSCl-C2), and 32 (BSCl-C3) and acceptor IDIC-4Cl pure films; (e~g) 2D GIWAXS patterns of blended films under optimized conditions; (h) 1D GIWAXS curves of 30, 31, 32 and IDIC-4Cl pure and blended films under optimized conditions; B: (a~c) TEM images of blended films based on different donors 30, 31, and 32; (d~f) corresponding AFM height images. Copyright 2020, American Chemical Society[62].

图5. A: 单组分膜和混合膜的AFM高度图 (a) 单组分42 (BOHTR)膜, (b) 单组分41 (BIHTR)膜, (c) 42:Y6混合膜, (d) 41:Y6混合膜, (e~h) 它们对应的相分离图像; B: (a, b) 单组分膜42和41在热退火后的GIWAXS 2D衍射图案; (c, d) 42:Y6和41:Y6混合膜的GIWAXS 2D衍射图案; C: HAAD-STEM图像 (a) 42:Y6, (b) 41:Y6混合膜. 版权2019, WILEY-VCH[67].

Figure 5. A: AFM height images of pure and blend films (a) pure 42 (BOHTR) film, (b) pure 41 (BIHTR) film, (c) 42:Y6 blend film, and (d) 41:Y6 blend film, and (e~h) their corresponding phase images; B: (a, b) GIWAXS 2D diffraction patterns of 42 and 41 pure films after TA; (c, d) GIWAXS 2D diffraction patterns of 42:Y6 and 41:Y6 blends; C: HAAD-STEM images of (a) 42:Y6 and (b) 41:Y6 blend films. Copyright 2019, WILEY-VCH[67].

图6. 萘并二噻吩和二噻并苯并二并噻吩类小分子电子给体材料的化学结构

Figure 6. Chemical structures of NDT and DTBDT-based small molecule electron donors

Donor	HOMO/LUMO (eV)	E_g^a/eV	Acceptor	μ_h×10^–4/ (cm²·V^–1·s^–1)	V_oc/V	J_sc/(mA·cm^–2)	FF/%	PCE/%	Reference
46	-5.23/-3.50	1.73	IDIC	0.486	0.89	13.20	56.60	6.60	[83]
47	-5.25/-3.50	1.73	ITIC	0.0676	1.00	5.36	32.85	1.77	[84]
47	-5.25/-3.50	1.73	IDIC	1.18	0.92	14.13	61.95	8.05	[84]
48	-5.25/-3.46	1.83	IDIC-4F	3.01	0.76	17.02	71.40	9.20	[86]
49	-5.26/-3.46	1.82	IDIC-4F	3.69	0.78	18.89	72.80	10.40	[86]
50	-5.27/-3.41	1.82	IDIC-4F	5.60	0.77	14.28	54.41	6.11	[87]
51	-5.34/-3.46	1.82	IDIC-4F	1.69	0.79	15.02	59.58	7.06	[87]

表2. 萘并二噻吩类小分子电子给体材料在ASM-OSCs中的光伏性能

Table 2. Photovoltaic properties of NDT-based small molecule electron donors in ASM-OSCs

图7. A: 48 (NDT-3T-R4):IDIC-4F和49 (NDT-3T-R6):IDIC-4F混合膜的AFM相分离图像和TEM图像; B: (a~e) 单组分膜和混合膜的2D GIWAXS图案, (f) 混合膜的GIWAXS面外切割曲线. 版权2018, WILEY-VCH[86].

Figure 7. A: AFM phase images and TEM images of the 48 (NDT-3T -R4):IDIC-4F and 49 (NDT-3T-R6):IDIC-4F blended films; B: (a~e) 2D GIWAXS patterns of the pure and blended films, (f) out-of-plane cuts of the GIWAXS patterns of the blended films. Copyright 2018, WILEY-VCH[86].

Donor	HOMO/LUMO (eV)	E_g^a/eV	Acceptor	μ_h×10^–4/ (cm²·V^–1·s^–1)	V_oc/V	J_sc/(mA·cm^–2)	FF/%	PCE/%	Reference
52	-5.11/-3.43	1.68	O-IDTBR	2.26	0.76	13.28	41.00	4.20	[97]
53	-5.17/-3.49	1.68	O-IDTBR	2.97	0.78	8.07	43.00	2.72	[97]
54	-5.36/-3.55	1.85	Y6	0.673	0.848	21.35	65.12	11.79	[98]
55	-5.35/-3.51	1.83	Y6	0.778	0.852	23.03	65.43	12.84	[98]
56	-5.34/-3.50	1.81	Y6	1.52	0.854	24.69	70.06	14.78	[98]
57	-5.32/-3.53	1.84	IDIC-4Cl	4.29	0.776	18.27	67.96	9.64	[99]
58	-5.50/-3.60	1.85	IDIC-4Cl	4.30	0.868	18.30	68.03	10.81	[99]
59	-5.56/-3.60	1.87	IDIC-4Cl	5.62	0.885	19.78	68.81	12.05	[99]
57	-5.32/-3.53	1.84	IDIC-4Cl	3.30	0.776	18.27	67.96	9.64	[107]
57	-5.32/-3.53	1.84	Y6	1.32	0.861	24.34	68.44	14.34	[107]

表3. 二噻并苯并二噻吩类小分子电子给体材料在ASM-OSCs中的光伏性能

Table 3. Photovoltaic properties of DTBDT-based small molecule electron donors in ASM-OSCs

图8. A: Y6体系BHJ混合膜的GIWAXS数据; 无后处理的54 (ZR2-C1:Y6)混合膜的2D GIWAXS图像, (d) 有后处理的; (b) 无后处理的55 (ZR2-C2:Y6)混合膜, (e) 有后处理的; (c) 无后处理的56 (ZR2-C3:Y6), (f) 有后处理的; (g) 混合膜2D GIWAXS的面内面外切割曲线; B: (a) 无后处理混合膜54:Y6的TEM图像, (d)有后处理的; (b) 无后处理的混合膜55:Y6, (e) 有后处理的; (c) 无后处理的混合膜56:Y6, (f, g) 有后处理的; (h) 混合膜中多级次形貌的示意图. 版权2020, Wiley-VCH GmbH[98].

Figure 8. A: GIWAXS data for BHJ blend films in Y6 systems. Two-dimensional GIWAXS image of 54 (ZR2-C1:Y6) as-prepared and (d) after annealing; (b) 55 (ZR2-C2:Y6) as-prepared and (e) after annealing; (c) 56 (ZR2-C3:Y6) as-prepared and (f) after annealing; (g) in-plane patterns and out-of-plane patterns of two-dimensional GIWAXS of the blending films; B: (a) TEM images of 54:Y6 as-prepared and (d) after annealing; (b) 55:Y6 as-prepared and (e) after annealing; (c) 56:Y6 as-prepared and (f, g) after annealing. (h) Illustration of the hierarchical morphology in the blending films. Copyright 2020, Wiley-VCH GmbH[98].

图9. A: 单组分膜和混合膜的微观结构; (a~f) 单组分膜和混合膜的2D GIWAXS图案; (g) 相应的面内面外切割曲线; (h) 57 (ZR1)小分子在它的单晶中垂直于二聚体的π堆积的视图; (i) 沿着π堆积方向; B: 57:Y6和57:IDIC-4Cl混合膜的形貌分析; (a~f) 混合膜在不同退火温度下的TEM图像, 其尺寸大都在200 nm. 版权2019, Springer Nature[107].

Figure 9. A: Microstructures of pristine and blend films. (a~f) 2D GIWAXS patterns of pristine and blend films; (g) Corresponding out-of-plane curves and in-plane curves; (h) View of perpendicular to π-stacking of dimers of 57 (ZR1) molecules in its single crystal and (i) along the π-stacking direction; B: Morphology analysis of 57:Y6 and 57:IDIC-4Cl blends; (a~f) TEM images of blends films obtained at different annealing temperatures, and the scale bars are all 200 nm. Copyright 2019, Springer Nature [107].

图10. AFM图像: (2×2 μm) (a) 膜里无PC71BM, (b) 膜内有PC71BM, 尺寸都是400 nm; TEM图像: (c) 膜没有PC71BM, (d) 膜有PC71BM, 尺寸是200 nm; 2D GIWAXS图案: (e) 膜里无PC71BM, (f) 膜里有PC71BM. 版权2020, 英国皇家化学学会[15].

Figure 10. AFM images (2×2 μm) of (a) film w/o PC71BM, and (b) film with PC71BM; the scale bars are 400 nm; TEM images of (c) film w/o PC71BM, and (d) film with PC71BM, the scale bars are 200 nm; 2D GIWAXS patterns of (e) film w/o PC71BM, and (f) film with PC71BM. Copyright 2020, The Royal Society of Chemistry[15].

图11. 本综述中介绍到的小分子受体材料的化学结构

Figure 11. Chemical structures of small molecule acceptors introduced in this review

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	( 代水星, 占肖卫, 高分子学报, 2017,1706.)

高结晶性小分子给体材料应用于全小分子有机太阳能电池中的研究进展

Research Progress of Small Molecule Donors with High Crystallinity in All Small Molecule Organic Solar Cells

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