空间构型和溴取代对三联芴放大自发辐射行为的影响

doi:10.6023/A24010012

摘要/Abstract

有机发光材料因其低成本、可溶液加工、机械灵活性和易于调控的光电特性而备受关注, 被广泛应用于有机发光二极管、有机固体激光器和荧光成像等领域. 然而, 有机激光增益介质普遍存在载流子迁移率低、三重态和极化子寿命长和宽吸收以及稳定性差等问题, 阻碍了有机电泵浦激光的实现. 通过引入大体积空间位阻基团可抑制发光分子间的相互作用, 减弱材料的发光猝灭效应, 有效提高发光效率. 设计合成了两种具有不同空间构型的芴基寡聚物HTF和ITF, 其放大自发辐射(ASE)阈值分别为6.67和12.35 µJ/cm². 其中, 寡聚物HTF展现更高的热稳定性、更小的温度依赖性和膜厚依赖性. 此外, 还发现溴原子的取代对二者ASE特性具有不同程度的负面影响.

关键词: 有机激光, 放大自发辐射, 增益介质, 空间位阻, 芴

Organic luminescent materials have garnered substantial attention within the scientific community owing to their notable attributes, encompassing cost-effectiveness, solution processability, mechanical flexibility, and easily adjustable optoelectronic properties. This multifaceted appeal has propelled their extensive adoption across a spectrum of applications, ranging from organic light-emitting diodes (OLEDs) and organic solid-state lasers (OSSL) to fluorescence imaging methodologies. Nevertheless, the advancement of organic electrically pumped lasers encounters significant hurdles. Organic gain media frequently grapple with challenges such as restricted charge carrier mobility, extended lifetimes of triplet states and polarons, broad absorption profiles, and inadequate stability, all of which pose substantial barriers to the practical realization of these laser systems. In response to these challenges, this study endeavors to introduce voluminous spatial hindrance groups as a prospective solution. These groups are strategically integrated to hinder intermolecular interactions among luminescent molecules, thereby alleviating the inherent luminescent quenching effects of the materials. This intervention not only augments luminescent efficiency but also fortifies the material's stability, addressing pivotal concerns within the discipline. The research methodology encompasses the design and synthesis of two distinct fluorene-based oligomers, namely HTF and ITF, each distinguished by unique spatial configurations. A meticulous examination of their amplified spontaneous emission (ASE) characteristics is conducted under diverse test conditions, incorporating dependencies on annealing temperature and film thickness. The minimum ASE thresholds for HTF and ITF are meticulously determined to be 6.67 and 12.35 µJ/cm², respectively. Furthermore, comparative analyses between HTF and ITF illuminate the distinctive performance attributes of each oligomer. Notably, HTF exhibits superior thermal stability, diminished temperature dependence, and reduced reliance on film thickness in contrast to ITF. Additionally, an evaluation of dibromo-substituted derivatives unveils variable degrees of negative impact on the ASE characteristics of both oligomers following bromine atom substitution, with ITF demonstrating a more pronounced susceptibility. Overall, this comprehensive investigation not only yields valuable insights into the structural design and performance modulation of organic laser gain media but also presents promising avenues for optimizing their efficiency and stability within the domain of optically pumped organic lasers.

Key words: organic laser, amplified spontaneous emission, gain media, steric hindrance, fluorine

引用此文

冯全友, 张云龙, 李昊, 李倩意, 沈建平, 虞梦娜, 解令海. 空间构型和溴取代对三联芴放大自发辐射行为的影响[J]. 化学学报, 2024, 82(4): 435-442.

Quanyou Feng, Yunlong Zhang, Hao Li, Qianyi Li, Jianping Shen, Mengna Yu, Linghai Xie. Geometry Configuration and Bromo Substitution Effect of Terfluorenes on Amplified Spontaneous Emission Behaviors[J]. Acta Chimica Sinica, 2024, 82(4): 435-442.

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图/表 10

图1. HTF、HTF-Br、ITF和ITF-Br的分子结构

Figure 1. Molecular structures of HTF, HTF-Br, ITF and ITF-Br

图2. HTF、HTF-Br、ITF-Br和ITF四种材料的薄膜吸收、发射和ASE光谱

Figure 2. Absorption, emission, and ASE spectra of HTF, HTF-Br, ITF-Br and ITF films

Compound	λ_abs^a/nm	λ_0-0^b/nm	λ_0-1^b/nm	λ_0-2^b/nm
HTF	355	411	429	456
HTF-Br	355	416	431	458
ITF	361	423	441	470
ITF-Br	366	428	446	500

表1. HTF、HTF-Br、ITF-Br和ITF四种材料薄膜的最大吸收峰和特征发射峰波长

Table 1. Maximum absorption and characteristic emission peak wavelengths of HTF, HTF-Br, ITF-Br and ITF films

图3. ASE光谱的FWHM和发射强度与泵浦能量的关系: (a) HTF-120 ℃; (b) ITF-120 ℃; (c) HTF-Br-90 ℃; (d) HTF和ITF两种材料薄膜的ASE阈值随退火温度变化的示意图

Figure 3. Dependence of FWHM and the peak intensity of the ASE spectra on the pump laser energy: (a) HTF-120 ℃; (b) ITF-120 ℃; (c) HTF-Br-90 ℃; (d) schematic diagram of the ASE thresholds of HTF and ITF films as a function of annealing temperatures

Compound	60 ℃	90 ℃	120 ℃	150 ℃	180 ℃	210 ℃	240 ℃
HTF	15.18	16.38	9.43	15.25	19.22	22.31	113.04
ITF	17.10	24.08	15.05	18.32	63.46	94.94	164.33
HTF-Br	—	479.08	—	—	—	—	—
ITF-Br	—	—	—	—	—	—	—

表2. 不同退火温度下, HTF、HTF-Br、ITF-Br和ITF四种材料的ASE阈值(μJ/cm2)

Table 2. ASE thresholds (μJ/cm2) for HTF, HTF-Br, ITF-Br and ITF under various annealing temperatures

图4. 不同退火温度下的ASE光谱: (a) HTF, (b) ITF

Figure 4. ASE spectra under various annealing temperatures: (a) HTF, (b) ITF

图5. 不同退火温度下的吸收和发射光谱: (a) HTF, (b) ITF

Figure 5. Absorption and emission spectra under various annealing temperatures: (a) HTF, (b) ITF

图6. 不同退火温度下的瞬态荧光衰减曲线: (a) HTF, (b) ITF, (c)汇总图

Figure 6. Transient fluorescence decay curves under various annealing temperatures: (a) HTF, (b) ITF, and (c) summary plots

图7. (a) HTF和(b) ITF薄膜的光稳定性(泵浦能量为10 μJ/pulse). 不同薄膜膜厚下, (c) HTF和(d) ITF的膜厚依赖性, 内嵌图为不同膜厚对应的ASE光谱

Figure 7. Photostability of (a) HTF and (b) ITF films under a pump energy of 10 μJ/pulse. Film thickness dependence of (c) HTF and (d) ITF under varying film thicknesses. Insets: ASE spectra for different film thicknesses

图8. ITF的合成路线

Figure 8. Synthetic route of ITF

参考文献 54

[1]	Xu, J.; Lin, A.; Yu, X.; Song, Y.; Kong, M.; Qu, F.; Han, J.; Jia, W.; Deng, N. IEEE Photon. 2016, 28, 2133.
[2]	Du, Q.; Liu, L.; Tang, R.; Ai, J.; Wang, Z.; Fu, Q.; Li, C.; Chen, Y.; Feng, X. Adv. Mater. Technol. 2021, 6, 2100122. doi: 10.1002/admt.v6.9
[3]	Liu, Y.; Yang, W.; Xiao, S.; Zhang, N.; Fan, Y.; Qu, G.; Song, Q. ACS Nano 2019, 13, 10653. doi: 10.1021/acsnano.9b04925
[4]	Restuccia, N.; Silipigni, L.; Cordaro, M.; Torrisi, L. Plasma Sci. Technol. 2019, 6, 1.
[5]	Partovi, A.; Peale, D.; Wuttig, M.; Murray, C. A.; Zydzik, G.; Hopkins, L.; Baldwin, K.; Hobson, W. S.; Wynn, J.; Lopata, J.; Dhar, L.; Chichester, R.; Yeh, J. H. J. Appl. Phys. Lett. 1999, 75, 1515. doi: 10.1063/1.124740
[6]	Zhang, Q.; Zeng, W.-J.; Xia, R.-D. Acta Phys. Sin. 2015, 64, 094202. (in Chinese) doi: 10.7498/aps
	(张琪, 曾文进, 夏瑞东, 物理学报, 2015, 64, 094202).
[7]	Qian, Y.; Wei, Q.; Del Pozo, G.; Mroz, M. M.; Luer, L.; Casado, S.; Cabanillas-Gonzalez, J.; Zhang, Q.; Xie, L.; Xia, R.; Huang, W. Adv. Mater. 2014, 26, 2937. doi: 10.1002/adma.v26.18
[8]	Soffer, B. H.; McFarland, B. B. Appl. Phys. Lett. 1967, 10, 266. doi: 10.1063/1.1754804
[9]	Wang, L.; Wu, J.; Yan, C.; Yang, W.; Che, Z.; Xia, X.; Wang, X.; Liao, L. Chin. Chem. Lett. 2023, 109365.
[10]	Zhuo, Z.; Wei, C.; Ni, M.; Cai, J.; Bai, L.; Zhang, H.; Zhao, Q.; Sun, L.; Lin, J.; Liu, W.; Ding, X.; Shen, K.; Huang, W. Dyes Pigm. 2022, 204, 110425. doi: 10.1016/j.dyepig.2022.110425
[11]	Karl, N. Phys. Status Solidi 1972, 13, 651. doi: 10.1002/(ISSN)1521-396X
[12]	Moses, D. Appl. Phys. Lett. 1992, 60, 3215. doi: 10.1063/1.106743
[13]	Sandanayaka, A. S.; Matsushima, T.; Bencheikh, F.; Terakawa, S.; Potscavage, W. J.; Qin, C.; Fujihara, T.; Goushi, K.; Ribierre, J.-C.; Adachi, C. Appl. Phys. Express 2019, 12, 061010. doi: 10.7567/1882-0786/ab1b90
[14]	Sandanayaka, A. S.; Matsushima, T.; Bencheikh, F.; Yoshida, K.; Inoue, M.; Fujihara, T.; Goushi, K.; Ribierre, J.-C.; Adachi, C. Sci. Adv. 2017, 3, e1602570. doi: 10.1126/sciadv.1602570
[15]	Wang, K.; Zhao, Y. S. Chem 2021, 7, 3221. doi: 10.1016/j.chempr.2021.10.014
[16]	Lin, D.; Liu, J.; Zhang, H.; Qian, Y.; Yang, H.; Liu, L.; Ren, A.; Zhao, Y.; Yu, X.; Wei, Y.; Hu, S.; Li, L.; Li, S.; Sheng, C.; Zhang, W.; Chen, S.; Shen, J.; Liu, H.; Feng, Q.; Wang, S.; Xie, L.; Huang, W. Adv. Mater. 2022, 34, e2109399.
[17]	Jiang, Y.; Liu, Y. Y.; Liu, X.; Lin, H.; Gao, K.; Lai, W. Y.; Huang, W. Chem. Soc. Rev. 2020, 49, 5885. doi: 10.1039/D0CS00037J
[18]	Thomas, S. Nat. Electron. 2023, 6, 721. doi: 10.1038/s41928-023-01060-5
[19]	Baldo, M. A.; Holmes, R. J.; Forrest, S. R. Phys. Rev. B 2002, 66, 035321. doi: 10.1103/PhysRevB.66.035321
[20]	Liu, J.; Zhang, H.; Dong, H.; Meng, L.; Jiang, L.; Jiang, L.; Wang, Y.; Yu, J.; Sun, Y.; Hu, W.; Heeger, A. J. Nat. Commun. 2015, 6, 10032. doi: 10.1038/ncomms10032
[21]	Feng, Q.; Xie, S.; Tan, K.; Zheng, X.; Yu, Z.; Li, L.; Liu, B.; Li, B.; Yu, M.; Yu, Y.; Zhang, X.; Xie, L.; Huang, W. ACS. Appl. Polym. Mater. 2019, 1, 2441. doi: 10.1021/acsapm.9b00559
[22]	Troisi, A.; Orlandi, G. J. Phys. Chem. 2006, 110, 4065. doi: 10.1021/jp055432g
[23]	Zhang, W.; Yan, Y.; Gu, J.; Yao, J.; Zhao, Y. S. Angew. Chem. Int. Ed. 2015, 54, 7125. doi: 10.1002/anie.201502684 pmid: 25925895
[24]	Qiao, C.; Zhang, C.; Zhou, Z.; Yao, J.; Zhao, Y. S. CCS Chem. 2022, 4, 250. doi: 10.31635/ccschem.021.202000768
[25]	Ou, Q.; Peng, Q.; Shuai, Z. Nat. Commun. 2020, 11, 4485. doi: 10.1038/s41467-020-18144-x
[26]	Wu, C.; DeLong, M.; Vardeny, Z.; Ferraris, J. Synth. Met. 2003, 137, 939. doi: 10.1016/S0379-6779(02)01192-X
[27]	Wu, L.; Casado, S.; Romero, B.; Otón, J. M.; Morgado, J.; Müller, C.; Xia, R.; Cabanillas-Gonzalez, J. Macromolecules 2015, 48, 8765. doi: 10.1021/acs.macromol.5b02111
[28]	Laquai, F.; Mishra, A. K.; Müllen, K.; Friend, R. H. Adv. Funct. Mater. 2008, 18, 3265. doi: 10.1002/adfm.v18:20
[29]	Aimono, T.; Kawamura, Y.; Goushi, K.; Yamamoto, H.; Sasabe, H.; Adachi, C. Appl. Phys. Lett. 2005, 86, 071110. doi: 10.1063/1.1867555
[30]	Sandanayaka, A. S. D.; Matsushima, T.; Bencheikh, F.; Terakawa, S.; Potscavage, W. J.; Qin, C.; Fujihara, T.; Goushi, K.; Ribierre, J.-C.; Adachi, C. Appl. Phys. Express 2019, 12, 061010. doi: 10.7567/1882-0786/ab1b90
[31]	Campoy-Quiles, M.; Ferenczi, T.; Agostinelli, T.; Etchegoin, P.; Kim, Y.; Anthopoulos, T. Nat. Mater. 2008, 7, 158. doi: 10.1038/nmat2102 pmid: 18204451
[32]	Kim, H.; Schulte, N.; Zhou, G.; Müllen, K.; Laquai, F. Adv. Mater. 2011, 23, 894. doi: 10.1002/adma.v23.7
[33]	Yu, M.-N.; Ou, C.-J.; Liu, B.; Lin, D.-Q.; Liu, Y.-Y.; Xue, W.; Lin, Z.-Q.; Lin, J.-Y.; Qian, Y.; Wang, S.-S.; Cao, H.-T.; Bian, L.-Y.; Xie, L.-H.; Huang, W. Chinese J. Polym. Sci. 2016, 35, 155. doi: 10.1007/s10118-017-1897-6
[34]	Huo, Y.; Fang, X.; Huang, B.; Zhang, K.; Nie, X.; Zeng, H. Chinese J. Org. Chem. 2012, 32, 1169. (in Chinese)
	(霍延平, 方小明, 黄宝华, 张焜, 聂晓李, 曾和平, 有机化学, 2012, 32, 1169). doi: 10.6023/cjoc201204021
[35]	Feng, Q.-Y.; Li, B.; Zuo, Z.-Y.; Xie, S.-L.; Yu, M.-N.; Liu, B.; Wei, Y.; Xie, L.-H.; Xia, R.-D.; Huang, W. Chinese J. Polym. Sci. 2018, 37, 11. doi: 10.1007/s10118-018-2152-5
[36]	Chang, Y.; Cao, H.; Feng, Q.; Wei, Y.; Bian, L.; Ling, H.; Lin, D.; Xie, L.; Huang, W. Sci. Bull. 2021, 66, 4268.
[37]	Xia, R.; Lai, W.-Y.; Levermore, P. A.; Huang, W.; Bradley, D. D. C. Adv. Funct. Mater. 2009, 19, 2844. doi: 10.1002/adfm.v19:17
[38]	Kanibolotsky, A. L.; Berridge, R.; Skabara, P. J.; Perepichka, I. F.; Bradley, D. D.; Koeberg, M. J. Am. Chem. Soc. 2004, 126, 13695. doi: 10.1021/ja039228n pmid: 15493927
[39]	Choi, E. Y.; Mazur, L.; Mager, L.; Gwon, M.; Pitrat, D.; Mulatier, J. C.; Monnereau, C.; Fort, A.; Attias, A. J.; Dorkenoo, K.; Kwon, J. E.; Xiao, Y.; Matczyszyn, K.; Samoc, M.; Kim, D. W.; Nakao, A.; Heinrich, B.; Hashizume, D.; Uchiyama, M.; Park, S. Y.; Mathevet, F.; Aoyama, T.; Andraud, C.; Wu, J. W.; Barsella, A.; Ribierre, J. C. Phys. Chem. Chem. Phys. 2014, 16, 16941. doi: 10.1039/c4cp01134a pmid: 25005146
[40]	Ribierre, J. C.; Zhao, L.; Inoue, M.; Schwartz, P. O.; Kim, J. H.; Yoshida, K.; Sandanayaka, A. S.; Nakanotani, H.; Mager, L.; Mery, S.; Adachi, C. Chem. Commun. 2016, 52, 3103. doi: 10.1039/C5CC08331A
[41]	Zuo, Z.; Ou, C.; Ding, Y.; Zhang, H.; Sun, S.; Xie, L.; Xia, R.; Huang, W. J. Mater. Chem. C 2018, 6, 4501. doi: 10.1039/C8TC00714D
[42]	Xu, W.; Yi, J.; Lai, W.-Y.; Zhao, L.; Zhang, Q.; Hu, W.; Zhang, X.-W.; Jiang, Y.; Liu, L.; Huang, W. Adv. Funct. Mater. 2015, 25, 4617. doi: 10.1002/adfm.v25.29
[43]	Navarro-Fuster, V.; Calzado, E. M.; Boj, P. G.; Quintana, J. A.; Villalvilla, J. M.; Díaz-García, M. A.; Trabadelo, V.; Juarros, A.; Retolaza, A.; Merino, S. Appl. Phys. Lett. 2010, 97, 171104. doi: 10.1063/1.3506500
[44]	Gayathri, P.; Karthikeyan, S.; Moon, D.; Anthony, S. P. ChemistrySelect 2019, 4, 3884. doi: 10.1002/slct.v4.13
[45]	Lin, J.-Y.; Zhu, W.-S.; Liu, F.; Xie, L.-H.; Zhang, L.; Xia, R.; Xing, G.-C.; Huang, W. Macromolecules 2014, 47, 1001. doi: 10.1021/ma402585n
[46]	Lin, D.; Li, Y.; Zhang, H.; Zhang, S.; Gao, Y.; Zhai, T.; Hu, S.; Sheng, C.; Guo, H.; Xu, C.; Wei, Y.; Li, S.; Han, Y.; Feng, Q.; Wang, S.; Xie, L.; Huang, W. Research 2023, 6, 0027. doi: 10.34133/research.0027
[47]	Yoshida, K.; Gong, J.; Kanibolotsky, A. L.; Skabara, P. J.; Turnbull, G. A.; Samuel, I. D. Nature 2023, 621, 746. doi: 10.1038/s41586-023-06488-5
[48]	Gan, S.; Hu, S.; Li, X. L.; Zeng, J.; Zhang, D.; Huang, T.; Luo, W.; Zhao, Z.; Duan, L.; Su, S. J.; Tang, B. Z. ACS Appl. Mater. Interfaces 2018, 10, 17327. doi: 10.1021/acsami.8b05389
[49]	Zhou, Z.; Qiao, C.; Wang, K.; Wang, L.; Liang, J.; Peng, Q.; Wei, Z.; Dong, H.; Zhang, C.; Shuai, Z. Angew. Chem. Int. Ed. 2020, 59, 21677. doi: 10.1002/anie.v59.48
[50]	Xu, M.; Wang, W.-B.; Bai, L.-B.; Yu, M.-N.; Han, Y.-M.; Lin, J.-Y.; Zhang, X.-W.; Ling, H.-F.; Lin, Z.-Q.; Huang, L.; Xie, L.-H.; Zhao, J.-F.; Wang, J.-P.; Huang, W. J. Mater. Chem. C 2018, 6, 7018. doi: 10.1039/C8TC01431K
[51]	Xu, M.; Wei, C.; Zhang, Y.; Li, H.; Ma, J.; Lin, J.; Wang, S.; Xue, W.; Wei, Q.; Xie, L.; Huang, W. Chin. Chem. Lett. 2024, 35, 108279. doi: 10.1016/j.cclet.2023.108279
[52]	Giebink, N. C.; Forrest, S. R. Phys. Rev. B 2009, 79, 073302. doi: 10.1103/PhysRevB.79.073302
[53]	Calzado, E. M.; Villalvilla, J. M.; Boj, P. G.; Quintana, J. A.; Díaz-García, M. A. J. Appl. Phys. 2005, 97, 093103. doi: 10.1063/1.1886891
[54]	Zhang, Z.-Y.; Xiao, Z.-H.; Zhu, S.; Zhang, Q.; Xia, R.-D.; Peng, J.-B. Acta Phys. Sin. 2023, 72, 214204. (in Chinese) doi: 10.7498/aps.72.20230773
	(张志远, 肖子晗, 邾珊, 张琪, 夏瑞东, 彭俊彪, 物理学报, 2023, 72, 214204).