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系统研究了水/醇溶性共轭聚电解质Poly[(9, 9-bis(3′-((N, N-dimethyl)-N-ethylammonium)-propyl)-2, 7-fluorene)-alt-2, 7-(9, 9-dioctylfluorene)]dibromide(PFN-Br)的光放大性质, 发现其具有较小的放大自发辐射(ASE)阈值(~11 μJ/cm2)和ASE截止厚度(<50 nm), 是一种高效的蓝光(~456 nm)增益介质. 利用其对于有机溶剂的良好耐性, 如甲苯等, 分别在石英和ITO玻璃基底上制备了PFN-Br/F8BT以及PFN-Br/MEH-PPV双层器件. 经过研究发现, PFN-Br界面层不会明显增加系统损耗并影响上层F8BT的光增益. 然而, 在ITO玻璃基底上, 通过引入PFN-Br界面层, 减少了ITO电极对MEH-PPV增益介质损耗, 显著地降低了其ASE阈值(相比于没有PFN-Br界面降低约60%). 这些发现说明了PFN-Br本身具备良好的增益性能, 同时也是成熟的载流子传输界面功能材料, 在有机激光领域应用前景十分广泛.In this paper, the optical gain properties of the water/alcohol soluble conjugated polyelectrolyte (Poly[(9,9-bis(3′-((N,N-dimethyl)-N-ethylammonium)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]) (PFN-Br) and its potential applications in future electrically pumped organic lasers are revealed and systematically studied. To the best of our knowledge, no studies on the optical gain properties of PFN-Br or its prototype, poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] have been reported before. These conjugated polyelectrolytes are widely used as the interlayers in organic light emitting diodes or organic solar cells. The thickness of such an interlayer is usually less than 10 nm, which is considered not sufficient for supporting light waveguiding. Therefore, the thickness of the PFN-Br layer used in this work is increased to more than 100 nm. Through careful study, the polymer is found to possess a low threshold of amplified spontaneous emission (ASE) (~11 μJ/cm2) and a small ASE cutoff thickness (<50 nm). It is an efficient blue emission (~456 nm) gain medium. The ASE peak of the PFN-Br film is red-shifted as the thickness increases from 50 to 220 nm. By utilizing the great resistance of PFN-Br against the organic solvent, such as toluene, PFN-Br/F8BT bilayer devices on quartz and PFN-Br/MEH-PPV bilayer devices on ITO glass are fabricated and characterized. In the PFN-Br/F8BT bilayer devices, it is found that the PFN-Br interlayer has very limited influence on F8BT. The ASE threshold of F8BT increases only twice, compared with that of F8BT monolayer device, when 100-nm-thick PFN-Br layer is introduced beneath the F8BT film. No significant change in optical gain or loss is observed. Most of the extra losses in F8BT due to the introduction of PFN-Br are attributed to the larger refractive index of PFN-Br than that of quartz substrate. Furthermore, in the PFN-Br/MEH-PPV bilayer devices on ITO glass, introducing PFN-Br interlayer resulting in optimal ASE performance of MEH-PPV compared with that on bare ITO surface. The ASE threshold of MEH-PPV is reduced as much as 60% (from 402 μJ/cm2 to 160 μJ/cm2) while the PFN-Br layer is sandwiched between ITO and MEH-PPV. The PFN-Br layer modifies the waveguiding modes, and reduces the interaction between excitons and ITO electrodes. As a result, the ASE performance of MEH-PPV is improved. The findings of this report indicate that the PFN-Br is not only a good carrier transport material but also a highly-efficient gain medium. PFN-Br, combined with its advantages in different fields, is expected to play various roles in future organic electrically pumped lasers.
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Keywords:
- organic semiconductor laser /
- amplified spontaneous emission /
- polymeric film /
- water soluble polymer
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Google Scholar
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图 1 在不同基底上利用PFN-Br做界面层, 改善常见非极性溶剂可溶聚合物增益介质性能的制备过程示意图
Fig. 1. Schematic diagram of fabrication processes of using PFN-Br as interlayer for modifying gain properties of the common non-polar solvent soluble polymeric gain mediums.
图 2 (a) PFN-Br薄膜的原子力显微镜(AFM)图; (b)甲苯冲涂后的PFN-Br薄膜AFM图
Fig. 2. (a) Atomic force microscope (AFM) diagram of PFN-Br film; (b) AFM diagram of PFN-Br film after toluene impact coating.
图 4 (a) PFN-Br薄膜的吸收和PL光谱; (b) F8BT薄膜的吸收、PL光谱和ASE光谱; (c) MEH-PPV薄膜的吸收、PL光谱和ASE光谱
Fig. 4. (a) Absorption and PL spectra of PFN-Br film; (b) absorption, PL, and ASE spectra of F8BT film; (c) absorption, PL, and ASE spectra of MEH-PPV film.
图 5 (a) PFN-Br薄膜(120 nm)的FWHM和输出强度随泵浦能量密度的变化; (b)不同泵浦能量下, PFN-Br的归一化发射光谱
Fig. 5. (a) FWHM and output intensity of PFN-Br thin film (120 nm) as a function of pump energy density; (b) normalized emission spectra of PFN-Br at different pump energy density.
图 6 (a)不同厚度的PFN-Br薄膜的ASE光谱; (b) PFN-Br薄膜的ASE阈值和ASE波长随膜厚的变化
Fig. 6. (a) ASE spectra of PFN-Br films with different thicknesses; (b) ASE threshold and ASE wavelength of PFN-Br films as a function of film thickness.
图 7 在石英基底上, 引入不同厚度PFN-Br界面层条件下, 测得的F8BT薄膜发射谱的(a) FWHM和(b)峰位强度随泵浦能量变化的示意图
Fig. 7. (a) FWHM and (b) peak intensities under different pump energies measured in F8BT films on quartz substrates with inserted PFN-Br interlayers of various thickness values.
图 8 在石英基底上, 不同PFN-Br厚度上F8BT薄膜的ASE光谱
Fig. 8. ASE spectra of F8BT films on quartz with inserted PFN-Br interlayers of different thickness values.
图 9 F8BT单层和PFN-Br(50 nm)/F8BT双层器件中F8BT薄膜的损耗
Fig. 9. Loss coefficient of F8BT in monolayer and PFN-Br (50 nm)/F8BT bilayer structures.
图 10 MEH-PPV在石英、玻璃以及在引入不同厚度PFN-Br界面层条件下ITO玻璃上测得的(a)发射谱半峰宽以及(b)发射峰强度随泵浦能量的变化
Fig. 10. (a) FWHM and (b) peak intensities measured in MEH-PPV films on ITO glass with inserted PFN-Br interlayers of different film thickness, compared with MEH-PPV monolayer on quartz and glass.
图 11 MEH-PPV薄膜在不同基底上以及在不同厚度PFN-Br薄膜上(ITO玻璃基底)的ASE光谱
Fig. 11. ASE spectra of MEH-PPV monolayer on different substrates and in bilayer devices with inserted PFN-Br interlayers of different thickness on ITO glass.
图 12 ITO基底的吸收光谱, 以及MEH-PPV薄膜分别在ITO玻璃和石英基底上的吸收光谱(已除去基底的吸收背景, 如插图)和PL光谱
Fig. 12. Absorption spectra of ITO substrates; the absorption spectra (small illustration) and PL spectra of MEH-PPV thin films on ITO glass and quartz, respectively.
表 1 不同溶液浓度和转速制备的薄膜
Table 1. Thin films prepared at different solution concentrations and rotational speeds.
材料 溶液浓度/
(mg·mL–1)转速/(r·min–1) 膜厚/nm PFN-Br 3 2000 15 PFN-Br 4 2000 30 PFN-Br 5 2000 50 PFN-Br 6 2000 65 PFN-Br 7 2000 100 PFN-Br 12 4000 120 PFN-Br 12 3000 130 PFN-Br 12 2000 160 PFN-Br 12 1500 170 PFN-Br 12 1000 220 F8BT 25 2000 160 MEH-PPV 25 2000 210 
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[1] Chenais S, Forget S 2012 Polym. Int. 61 390
Google Scholar
[2] Yap B K, Xia R D, Campoy-Quiles M, Stavrinou P N, Bradley D D C 2008 Nat. Mater. 7 376
Google Scholar
[3] Kim H, Schulte N, Zhou G, Mullen K, Laquai F 2011 Adv. Mater. 23 894
Google Scholar
[4] Feng Z J, Cheng Z, Jin H X, Lu P 2022 J. Mater. Chem. C Mater. 10 4497
Google Scholar
[5] Sarma M, Chen L M, Chen Y S, Wong K T 2022 Mater. Sci. Eng. R Rep. 150 100689
Google Scholar
[6] Al-Azzawi A G S, Aziz S B, Dannoun E M A, Iraqi A, Nofal M M, Murad A R, Hussein A M 2023 Polymers 15 164
Google Scholar
[7] Li B, Yang X, Li S Y, Yuan J Y 2023 Energy Environ. Sci. 16 723
Google Scholar
[8] Wang J J, Wen S G, Hu J, Han J H, Yang C P, Li J F, Bao X C, Yan S K 2022 Chem. Eng. J. 452 139462
Google Scholar
[9] Yazdani S A, Mikaeili A, Bencheikh F, Adachi C 2022 Jpn. J. Appl. Phys. 61 074003
Google Scholar
[10] Zhang Q, Tao W W, Huang J S, Xia R D, Cabanillas-Gonzalez J 2021 Adv. Photonics. Res. 2 2000155
Google Scholar
[11] He Z C, Zhong C M, Su S J, Xu M, Wu H B, Cao Y 2012 Nat. Photonics 6 591
Google Scholar
[12] Zhao Y Y, Zhang Q W, Liu Y F, Lv C, Guo S, Liu X P, Bi Y G, Li H W, Wu Y Q 2022 Org. Electron. 109 106620
Google Scholar
[13] Feng C, Wang X J, He Z C, Cao Y 2021 Sol. RRL 5 2000753
Google Scholar
[14] Hsu F C, Lin Y A, Li C P 2021 Org. Electron. 89 106008
Google Scholar
[15] Li M Q, Jiang J X, Ning Y J, Zhao S L, Masri W F A, Wageh S, Al-Ghamdi A 2022 Synth. Met. 289 117122
Google Scholar
[16] Hu Z C, Zhang K, Huang F, Cao Y 2015 Chem. Commun. 51 5572
Google Scholar
[17] Huang F, Wu H B, Wang D, Yang W, Cao Y 2004 Chem. Mater. 16 708
Google Scholar
[18] Wu H B, Huang F, Mo Y Q, Yang W, Wang D L Peng J B, Cao Y 2004 Adv. Mater. 16 1826
Google Scholar
[19] Fu J F, Yuan L G, Ling F, Duan R M, Chen Q Y, Ma H, Zhou M, Song B, Zhou Y, Li Y F 2020 J. Power Sources 449 227474
Google Scholar
[20] Xiong X, Xue X N, Zhang M, Hao T Y, Han Z Y, Sun Y Y, Zhang, Y M, Liu F, Pei S P, Zhu L 2021 ACS Energy Lett. 6 3582
Google Scholar
[21] Ohisa S, Kato T, Takahashi T, Suzuki M, Hayashi Y, Koganezawa T, McNeill C R, Chiba T, Pu Y J, Kido J 2018 ACS Appl. Mater. Interfaces 10 17318
Google Scholar
[22] Stevens M A, Silva C, Russell D M, Friend R H 2001 Phys. Rev. B 63 165213
Google Scholar
[23] Xia R D, Heliotis G, Bradley D D C 2003 Appl. Phys. Lett. 82 3599
Google Scholar
[24] Hayes G R, Samuel I D W, Phillips R T 1997 Synth. Met. 84 889
Google Scholar
[25] Kretsch K P, Belton C, Lipson S, Blau W J, Henari F Z, Rost H, Pfeiffer S, Teuschel, A, Tillmann H, Horhold H H 1999 J. Appl. Phys. 86 6155
Google Scholar
[26] Calzado E M, Villalvilla J M, Boj P G, Quintana J A, Diaz-Garcia M A 2005 J. Appl. Phys. 97 093103
Google Scholar
[27] Anni M, Perulli A, Monti G 2012 J. Appl. Phys. 111 093109
Google Scholar
[28] Heliotis G, Bradley D D C, Turnbull G A, Samuel I D W 2002 Appl. Phys. Lett. 81 415
Google Scholar
[29] Peng X, Liu L Y, Wu J F, Li Y G, Hou Z J, Xu L, Wang W C, Li F M 2000 Opt. Lett. 25 314
Google Scholar
[30] Feng Y J, Yu X L, Zhang R, Wu J W, Zhang P, Chen S J, Zhang, D K 2017 J. Alloys Compd. 729 513
Google Scholar
[31] 杜惠军, 李睿, 骆逸夫, 王竹君, 吴霞, 伊书颖, 皮明雨, 张丁可 2019 中国科学: 化学 49 1475
Du H J, Li R, Luo Y F, Wang Z J, Wu X, Yi S Y, Pi M Y, Zhang D K 2019 Sci. Sin. Chim. 49 1475
[32] Lahoz F, Oton C J, Capuj N, Ferrer-Gonzalez M, Cheylan S, Navarro-Urrios D 2009 Opt. Express 17 16766
Google Scholar
[33] Pauchard M, Swensen J, Moses D, Heeger A J, Perzon E, Andersson M R 2003 J. Appl. Phys. 94 3543
Google Scholar
[34] Haugeneder A, Neges M, Kallinger C, Spirkl W, Lemmer U, Feldmann J, Amann M C, Scherf U 1999 J. Appl. Phys. 85 1124
Google Scholar
[35] Reufer M, Feldmann J, Rudati P, Ruhl A, Muller D, Meerholz K, Karnutsch C, Gerken M, Lemmer U 2005 Appl. Phys. Lett. 86 221102
Google Scholar
[36] Therezio E M, Hidalgo A A, Oliveira O N, Silva R A, Marletta A 2015 J. Braz. Chem. Soc. 26 1798
Google Scholar
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