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Giant nonlinear Raman responses from organic semiconductors

Abstract

Organic semiconductors exhibit unique semiconducting behaviour due to *π-*electron delocalization along their molecular chains, making them attractive for various optoelectronic applications. However, their low optical damage thresholds have limited their use in nonlinear optics, particularly in stimulated Raman scattering. Here we demonstrate a general method to significantly amplify molecular vibrations in organic semiconductors by utilizing spectrally tailored gain from stimulated emission, bypassing the necessity for traditional optical cavities. This method achieves Raman thresholds as low as ~10–50 μJ cm−2 or ~2–10 kW cm−2, outperforming current Raman lasers by four orders of magnitude. The resulting nonlinear Raman response leads to cascaded Raman emission characterized by pump-dependent emission efficiency, a nonlinearity factor of 3.8, a signal-to-noise ratio of 30.9 dB and a bandwidth of 110 nm. Our study opens exciting prospects for the development of compact, efficient Raman amplifiers and lasers, leveraging the unique properties of organic semiconductors for advanced photonic applications, including high-sensitivity spectroscopy and versatile frequency conversion technologies.

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Fig. 1: Principle and design of multi-amplified Raman modes in organic semiconductors.

Fig. 2: Multiple STGI-SRS in the SpL(2)-1 film.

Fig. 3: Observation of multi-amplified Raman modes in the SpL(2)-1 film with 450 nm pumping.

Fig. 4: Tunable properties of cascaded STGI-SRS in the SpL(2)-1 film.

Fig. 5: Sensing performance through STGI-SRS signal detection in an SpL(2)-1 film exposed to DNT and TNT at 450 nm pumping.

Data availability

Source data are provided with this paper. Additional information is available from the authors on request.

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Acknowledgements

We acknowledge financial support from the National Key Research and Development Program of China (2024YFB3612500, 2024YFB3612600 and 2023YFB3608904), the National Natural Science Foundation of China (21835003, 91833304, 21422402 and 21674050), the National Key Basic Research Program of China (2017YFB0404501 and 2014CB648300), the Basic Research Program of Jiangsu Province (BK20243057), the Natural Science Foundation of Jiangsu Province (BE2019120), the Program for Jiangsu Specially-Appointed Professor (RK030STP15001 and RK119STP24001), the Foundation of Key Laboratory of Flexible Electronics of Zhejiang Province (2023FE002), the Leading Talent of Technological Innovation of National Ten-Thousands Talents Program of China, the Excellent Scientific and Technological Innovative Teams of Jiangsu Higher Education Institutions (TJ217038), the Synergetic Innovation Center for Organic Electronics and Information Displays and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD, YX030003). Y.J. thanks the Natural Science Foundation for Excellent Young Scholars (62404108), the Natural Science Foundation for Excellent Young Scholars of Jiangsu Province (BK20240636) and the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (NY223018) for support.

Author information

Author notes

These authors contributed equally: Yi Jiang, He Lin, Jin-Qiang Pan.

Authors and Affiliations

State Key Laboratory of Flexible Electronics (LoFE), Institute of Advanced Materials (IAM), School of Chemistry and Life Sciences, Nanjing University of Posts and Telecommunications, Nanjing, China

Yi Jiang, He Lin, Jin-Qiang Pan, Jia-Ling Zhang, Yang Wang, Zhan-Bo Jia, Xiang-Chun Li, Wei Huang & Wen-Yong Lai

Department of Physics and Institute of Advanced Materials, Hong Kong Baptist University, Hong Kong SAR, China

Yi Jiang, Hoi Lam Tam, King Fai Li, Yong Jie Huang & Kok Wai Cheah

Department of Applied Physics, Hong Kong Polytechnic University, Hong Kong SAR, China

Qi Wei, Sheung Mei Ng & Chee Leung Mak

Department of Chemistry, National University of Singapore, Singapore, Singapore

Luying Yi & Xiaogang Liu

Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, St Andrews, UK

Ifor D. W. Samuel

Frontiers Science Center for Flexible Electronics (FSCFE), MIIT Key Laboratory of Flexible Electronics (KLoFE), Northwestern Polytechnical University, Xi’an, China

Wei Huang

School of Flexible Electronics (SoFE), Sun Yat-sen University, Shenzhen, China

Wei Huang

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Yi Jiang

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Contributions

Y.J., K.W.C., X.L., W.H. and W.-Y.L. conceived the idea and designed the experiments. Y.J., H.L., J.-Q.P., J.-L.Z., Q.W. and Z.-B.J. conducted testing and data analysis on ASE and STGI-SRS experiments. Y.J., H.L.T. and K.F.L. performed the absorption, PL and PL excitation measurements at room and cryogenic temperatures. S.M.N. and C.L.M. helped with measuring the Raman spectra of these material samples. Y.J.H. performed the film morphology measurement. Y.J., Y.W. and X.-C.L. synthesized and characterized the two spirofused ladder-type materials. Y.J., L.Y., I. D. W. S., K.W.C., X.L., W.H. and W.-Y.L. wrote and commented on the paper. All authors discussed the results. W.-Y.L. led the project.

Corresponding authors

Correspondence to Kok Wai Cheah, Xiaogang Liu, Wei Huang or Wen-Yong Lai.

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Nature Materials thanks Anthony Daleo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work

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Supplementary information

Supplementary Information

Supplementary Figs. 1–36, Discussion, Table 1 and References.

Source data

Source Data Fig. 1

ASE and PL spectrum of PFO, SpL(2)-1 and SpL-1: output intensity against pump fluence for the given samples.

Source Data Fig. 2

The Raman spectrum of SpL(2)-1: Raman spectrum; stimulated Raman spectra; STGI-SRS against the frequency of the pump light.

Source Data Fig. 3

Emission spectra with increasing pump fluence; emission spectrum recorded at a pump fluence of 122 μJ cm−2; output intensity plotted as a function of pump fluence (PL/ASE, S00(5)); output intensity plotted as a function of pump fluence (double S00(5); triple S00(5)); SNR versus pump fluence; emission spectra for ASE and first-order STGI-SRS; emission spectra for second- and third- order STGI-SRS.

Source Data Fig. 4

STGI-SRS threshold as a function of emission wavelength; thresholds for first- to third-order STGI-SRS and ASE versus absorption coefficient; SNR on emission wavelength.

Source Data Fig. 5

Output intensity before and after a 5 min exposure to DNT; output intensity before and after a 5 min exposure to TNT; emission spectrum changes in the first-order STGI-SRS before and after a 5 min exposure to DNT; emission spectrum changes in the second-order STGI-SRS before and after a 5 min exposure to DNT; pump-fluence-dependent sensing efficiency for detecting DNT vapour.

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Jiang, Y., Lin, H., Pan, JQ. et al. Giant nonlinear Raman responses from organic semiconductors. Nat. Mater. (2025). https://doi.org/10.1038/s41563-025-02196-9

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Received:21 August 2023

Accepted:05 March 2025

Published:02 April 2025

DOI:https://doi.org/10.1038/s41563-025-02196-9

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