journal article·2025-11-28Open access

Photoluminescence enhancement by exciton-plasmon coupling in MAPbI3 quantum dots on gold nanorods

Tianci Wang, Tetsuro Katayama, Xu Shi, Akihiro Furube, Takuya Okamoto, Vasudevanpillai Biju

NPG Asia Materials· Volume 17· Issue 1

Abstract

Localized surface plasmon resonance (LSPR) is widely studied for its role in enhancing optical properties and facilitating charge or energy transfer through exciton-plasmon interactions in materials such as organic dyes, chalcogenide and halide perovskite quantum dots (PQDs), and transition-metal dichalcogenides (TMDCs). LSPR coupling with perovskite nanocrystals (PNCs) and quantum dots (QDs) has gained significant attention due to their outstanding electronic and optical properties. However, the precise effects of LSPR on the exciton dynamics of PQDs remain largely unexplored. This study focuses on exciton-plasmon coupling between gold nanorods (Au NRs) and individual methylammonium lead iodide (MAPbI₃) PQDs using single-particle blinking analysis. While PQDs without Au display a slow ON-OFF (long-lived ON and OFF states) blinking behavior, those on Au NRs exhibit short-lived, high-intensity ON states. This difference in blinking dynamics is attributed to energy transfer from Au NRs to PQDs through exciton-plasmon interactions and chemical interface damping. Further investigation through single-particle time-resolved photoluminescence measurements and ensemble-level transient absorption spectroscopy reveals that plasmon coupling enhances radiative recombination while expediting the ground-state bleach-recovery via energy transfer. Additionally, spatial variations in QD distributions on AU NRs are examined using transmission electron microscopy, high-resolution scanning transmission electron microscopy, and finite-difference time-domain simulations, providing deeper insight into the nature of exciton-plasmon interactions. This study explores how tiny particles called perovskite quantum dots (PQDs) interact with gold nanorods to enhance light emission. PQDs blink on and off when they emit ligh but when placed on gold nanorods, they emit brighter and more stable light. This is due to a phenomenon called exciton-plasmon coupling, where the PQDs and gold nanorods exchange energy. Researchers prepared PQDs without protective layers and observed their behavior on glass and gold nanorod surfaces. They used various techniques like single-particle imaging and time-resolved photoluminescence to study these interactions. The study found that PQDs on gold nanorods showed up to 13 times more intense light emission compared to those on glass. The findings suggest that this interaction can improve the performance of devices like solar cells and LEDs by making them more efficient in converting light into energy. This summary was initially drafted using artificial intelligence, then revised and fact-checked by the author. In this article, we explore the coupling between the localized surface plasmon of gold nanorods and the excitonic states of methylammonium lead iodide (MAPbI3) perovskite quantum dots. Using single-molecule fluorescence microscopy, time-resolved fluorescence spectroscopy, transient absorption spectroscopy, and finite-difference time-domain simulations, we reveal the origin of exciton-plasmon-coupled blinking suppression and emission intensity enhancement in the gold nanorod-MAPbI3 quantum dot system.
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Research context

OpenAlex topics: Perovskite Materials and Applications · Strong Light-Matter Interactions · Plasmonic and Surface Plasmon Research

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (65)

Show source-provided references
1. Barnes, W. L., Dereux, A. & Ebbesen, T. W. Surface plasmon subwavelength optics. Nature 424, 824–830 (2003).10.1038/nature01937 ↗
2. Ritchie, R. H. Plasma losses by fast electrons in thin films. Phys. Rev. 106, 874–881 (1957).10.1103/PhysRev.106.874 ↗
3. Cao, E., Lin, W., Sun, M., Liang, W. & Song, Y. Exciton-plasmon coupling interactions: from principle to applications. Nanophotonics 7, 145–167 (2018).10.1515/nanoph-2017-0059 ↗
4. Yin, H. et al. Plasmon enhanced quantum dots fluorescence and energy conversion in water splitting using shell-isolated nanoparticles. Nano Energy 42, 232–240 (2017).10.1016/j.nanoen.2017.10.055 ↗
5. Itoh, T. et al. Toward a new era of SERS and TERS at the nanometer scale: from fundamentals to innovative applications. Chem. Rev. 123, 1552–1634 (2023).10.1021/acs.chemrev.2c00316 ↗
6. Li, J. et al. Ultrasensitive plasmon-enhanced infrared spectroelectrochemistry. Angew. Chem. Int. Ed. 63, e202319246 (2024).10.1002/anie.202319246 ↗
7. Boerigter, C., Campana, R., Morabito, M. & Linic, S. Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis. Nat. Commun. 7, 10545 (2016).10.1038/ncomms10545 ↗
8. Sharma, D. K., Hirata, S., Biju, V. & Vacha, M. Stark effect and environment-induced modulation of emission in single halide perovskite nanocrystals. ACS Nano 13, 624–632 (2019).10.1021/acsnano.8b07677 ↗
9. Huang, H., Bodnarchuk, M. I., Kershaw, S. V., Kovalenko, M. V. & Rogach, A. L. Lead halide perovskite nanocrystals in the research spotlight: stability and defect tolerance. ACS Energy Lett. 2, 2071–2083 (2017).10.1021/acsenergylett.7b00547 ↗
10. Rainò, G. et al. Ultra-narrow room-temperature emission from single CsPbBr3 perovskite quantum dots. Nat. Commun. 13, 2587 (2022).10.1038/s41467-022-30016-0 ↗
11. Chouhan, L., Ghimire, S., Subrahmanyam, C., Miyasaka, T. & Biju, V. Synthesis, optoelectronic properties and applications of halide perovskites. Chem. Soc. Rev. 49, 2869–2885 (2020).10.1039/C9CS00848A ↗
12. Ghimire, S. et al. Amplified and multicolor emission from films and interfacial layers of lead halide perovskite nanocrystals. ACS Energy Lett. 4, 133–141 (2018).10.1021/acsenergylett.8b01916 ↗
13. Jang, Y. H. et al. Plasmonic solar cells: from rational design to mechanism overview. Chem. Rev. 116, 14982–15034 (2016).10.1021/acs.chemrev.6b00302 ↗
14. Wei, C. et al. A universal ternary-solvent-ink strategy toward efficient inkjet-printed perovskite quantum dot light-emitting diodes. Adv. Mater. 34, e2107798 (2022).10.1002/adma.202107798 ↗
15. Hsieh, Y. H. et al. Perovskite quantum dot lasing in a gap-plasmon nanocavity with ultralow threshold. ACS Nano 14, 11670–11676 (2020).10.1021/acsnano.0c04224 ↗
16. Wei, H. L. et al. High-performance CsPbI3 quantum dot photodetector with a vertical structure based on the Frenkel-Poole emission effect. ACS Nano 18, 26643–26654 (2024).10.1021/acsnano.4c05111 ↗
17. Erwin, W. R., Zarick, H. F., Talbert, E. M. & Bardhan, R. Light trapping in mesoporous solar cells with plasmonic nanostructures. Energy Environ. Sci. 9, 1577–1601 (2016).10.1039/C5EE03847B ↗
18. Mertens, H., Koenderink, A. F. & Polman, A. Plasmon-enhanced luminescence near noble-metal nanospheres: comparison of exact theory and an improved Gersten and Nitzan model. Phys. Rev. B 76, 115123 (2007).10.1103/PhysRevB.76.115123 ↗
19. Lalanne, P., Yan, W., Vynck, K., Sauvan, C. & Hugonin, J. P. Light interaction with photonic and plasmonic resonances. Laser Photonics Rev. 12, 1700113 (2018).10.1002/lpor.201700113 ↗
20. Purcell, E. M., Torrey, H. C. & Pound, R. V. Resonance absorption by nuclear magnetic moments in a solid. Phys. Rev. 69, 37–38 (1946).10.1103/PhysRev.69.37 ↗
21. Hartsfield, T. et al. Single quantum dot controls a plasmonic cavity’s scattering and anisotropy. Proc. Natl Acad. Sci. Usa. 112, 12288–12292 (2015).10.1073/pnas.1508642112 ↗
22. Lin, C. H. et al. Regulating the phase and optical properties of mixed-halide perovskites via hot-electron engineering. Adv. Funct. Mater. 34, 2402935 (2024).10.1002/adfm.202402935 ↗
23. Li, J. et al. Plasmon-induced resonance energy transfer for solar energy conversion. Nat. Photonics 9, 601–607 (2015).10.1038/nphoton.2015.142 ↗
24. Cushing, S. K. et al. Photocatalytic activity enhanced by plasmonic resonant energy transfer from metal to semiconductor. J. Am. Chem. Soc. 134, 15033–15041 (2012).10.1021/ja305603t ↗
25. Bitton, O., Gupta, S. N. & Haran, G. Quantum dot plasmonics: from weak to strong coupling. Nanophotonics 8, 559–575 (2019).10.1515/nanoph-2018-0218 ↗
26. Baranov, D. G., Wersäll, M., Cuadra, J., Antosiewicz, T. J. & Shegai, T. Novel nanostructures and materials for strong light–matter interactions. ACS Photonics 5, 24–42 (2017).10.1021/acsphotonics.7b00674 ↗
27. Lee, S. A. & Link, S. Chemical interface damping of surface plasmon resonances. Acc. Chem. Res. 54, 1950–1960 (2021).10.1021/acs.accounts.0c00872 ↗
28. Chouhan, L. et al. Real-time blinking suppression of perovskite quantum dots by halide vacancy filling. ACS Nano 15, 2831–2838 (2021).10.1021/acsnano.0c08802 ↗
29. Kim, T., Jung, S. I., Ham, S., Chung, H. & Kim, D. Elucidation of photoluminescence blinking mechanism and multiexciton dynamics in hybrid organic-inorganic perovskite quantum dots. Small 15, e1900355 (2019).10.1002/smll.201900355 ↗
30. Yuan, G., Gomez, D. E., Kirkwood, N., Boldt, K. & Mulvaney, P. Two mechanisms determine quantum dot blinking. ACS Nano 12, 3397–3405 (2018).10.1021/acsnano.7b09052 ↗
31. Ma, X., Tan, H., Kipp, T. & Mews, A. Fluorescence enhancement, blinking suppression, and gray states of individual semiconductor nanocrystals close to gold nanoparticles. Nano Lett. 10, 4166–4174 (2010).10.1021/nl102451c ↗
32. Ji, B. et al. Non-blinking quantum dot with a plasmonic nanoshell resonator. Nat. Nanotechnol. 10, 170–175 (2015).10.1038/nnano.2014.298 ↗
33. Karan, N. S. et al. Plasmonic giant quantum dots: hybrid nanostructures for truly simultaneous optical imaging, photothermal effect and thermometry. Chem. Sci. 6, 2224–2236 (2015).10.1039/C5SC00020C ↗
34. Ratchford, D., Shafiei, F., Kim, S., Gray, S. K. & Li, X. Manipulating coupling between a single semiconductor quantum dot and single gold nanoparticle. Nano Lett. 11, 1049–1054 (2011).10.1021/nl103906f ↗
35. He, Y. et al. Suppressed blinking and polarization-dependent emission enhancement of single ZnCdSe/ZnS dot coupled with Au nanorods. ACS Appl. Mater. Interfaces 14, 12901–12910 (2022).10.1021/acsami.2c00207 ↗
36. Wang, Z. et al. Bright nonblinking photoluminescence with blinking lifetime from a nanocavity-coupled quantum dot. Nano Lett. 24, 1761–1768 (2024).10.1021/acs.nanolett.3c04661 ↗
37. Jónsson, H. F. et al. Halogen bond activation in gold catalysis. ACS Catal. 12, 7210–7220 (2022).10.1021/acscatal.2c01864 ↗
38. Oliveira, V. & Cremer, D. Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes. Chem. Phys. Lett. 681, 56–63 (2017).10.1016/j.cplett.2017.05.045 ↗
39. Roman, B. J., Otto, J., Galik, C., Downing, R. & Sheldon, M. Au exchange or Au deposition: dual reaction pathways in Au-CsPbBr3 heterostructure nanoparticles. Nano Lett. 17, 5561–5566 (2017).10.1021/acs.nanolett.7b02355 ↗
40. Stefancu, A. et al. Halide–metal complexes at plasmonic interfaces create new decay pathways for plasmons and excited molecules. ACS Photonics 9, 895–904 (2022).10.1021/acsphotonics.1c01714 ↗
41. Pushkarev, A. P. et al. A few-minute synthesis of CsPbBr3 nanolasers with a high quality factor by spraying at ambient conditions. ACS Appl. Mater. Interfaces 11, 1040–1048 (2019).10.1021/acsami.8b17396 ↗
42. Zhang, F. et al. Colloidal synthesis of air-stable CH3NH3PbI3 quantum dots by gaining chemical insight into the solvent effects. Chem. Mater. 29, 3793–3799 (2017).10.1021/acs.chemmater.7b01100 ↗
43. Rabouw, F. T. et al. Delayed exciton emission and its relation to blinking in CdSe quantum dots. Nano Lett. 15, 7718–7725 (2015).10.1021/acs.nanolett.5b03818 ↗
44. Cichos, F., von Borczyskowski, C. & Orrit, M. Power-law intermittency of single emitters. Curr. Opin. Colloid Interface Sci. 12, 272–284 (2007).10.1016/j.cocis.2007.07.012 ↗
45. Knappenberger, K. L., Wong, D. B., Romanyuk, Y. E. & Leone, S. R. Excitation wavelength dependence of fluorescence intermittency in CdSe/ZnS core/shell quantum dots. Nano Lett. 7, 3869–3874 (2007).10.1021/nl0714740 ↗
46. Tang, J. & Marcus, R. A. Diffusion-controlled electron transfer processes and power-law statistics of fluorescence intermittency of nanoparticles. Phys. Rev. Lett. 95, 4 (2005).10.1103/PhysRevLett.95.107401 ↗
47. Tang, J. & Marcus, R. A. Mechanisms of fluorescence blinking in semiconductor nanocrystal quantum dots. J. Chem. Phys. 123, 12 (2005).10.1063/1.1993567 ↗
48. Cordones, A. A. & Leone, S. R. Mechanisms for charge trapping in single semiconductor nanocrystals probed by fluorescence blinking. Chem. Soc. Rev. 42, 3209–3221 (2013).10.1039/c2cs35452g ↗
49. Wang, T. et al. Highly controllable synthesis of MAPbI3 perovskite nanocrystals with long carrier lifetimes and narrow band gap for application in photodetectors. J. Alloy. Compd. 872, 159589 (2021).10.1016/j.jallcom.2021.159589 ↗
50. Dey, J., Virdi, A. & Chandra, M. Tuning nanoscale plasmon-exciton coupling via chemical interface damping. Nanoscale 15, 17879–17888 (2023).10.1039/D3NR04013E ↗
51. Nepal, D., Drummy, L. F., Biswas, S., Park, K. & Vaia, R. A. Large scale solution assembly of quantum dot-gold nanorod architectures with plasmon enhanced fluorescence. ACS Nano 7, 9064–9074 (2013).10.1021/nn403671q ↗
52. Sugimoto, H. et al. Plasmon-enhanced emission rate of silicon nanocrystals in gold nanorod composites. ACS Photonics 2, 1298–1305 (2015).10.1021/acsphotonics.5b00233 ↗
53. Zhang, M. et al. Investigation on the enhanced fluorescence emission from self-assembled Au nanorod film. Plasmonics 12, 1841–1845 (2016).10.1007/s11468-016-0452-6 ↗
54. Liu, X., Zeng, P., Chen, S., Smith, T. A. & Liu, M. Charge transfer dynamics at the interface of CsPbX3 perovskite nanocrystal-acceptor complexes: a femtosecond transient absorption spectroscopy study. Laser Photonics Rev. 16, 2200280 (2022).10.1002/lpor.202200280 ↗
55. Ashner, M. N. et al. Size-dependent biexciton spectrum in CsPbBr3 perovskite nanocrystals. ACS Energy Lett. 4, 2639–2645 (2019).10.1021/acsenergylett.9b02041 ↗
56. El-Ballouli, A. O. et al. Real-time observation of ultrafast intraband relaxation and exciton multiplication in PbS quantum dots. ACS Photonics 1, 285–292 (2014).10.1021/ph500016t ↗
57. Liu, G., Lou, Y., Zhao, Y. & Burda, C. Directional damping of plasmons at metal-semiconductor interfaces. Acc. Chem. Res. 55, 1845–1856 (2022).10.1021/acs.accounts.2c00001 ↗
58. Zhang, J., Zhu, B., Zhang, L. & Yu, J. Femtosecond transient absorption spectroscopy investigation into the electron transfer mechanism in photocatalysis. Chem. Commun. 59, 688–699 (2023).10.1039/D2CC06300J ↗
59. Zhang, Y. C. et al. Surface-plasmon-driven hot electron photochemistry. Chem. Rev. 118, 2927–2954 (2018).10.1021/acs.chemrev.7b00430 ↗
60. Staechelin, Y. U., Hoeing, D., Schulz, F. & Lange, H. Size-dependent electron-phonon coupling in monocrystalline gold nanoparticles. ACS Photonics 8, 752–757 (2021).10.1021/acsphotonics.1c00078 ↗
61. Nazir, A. Correlation-dependent coherent to incoherent transitions in resonant energy transfer dynamics. Phys. Rev. Lett. 103, 146404 (2009).10.1103/PhysRevLett.103.146404 ↗
62. Klimov, V. I., Mikhailovsky, A. A., McBranch, D. W., Leatherdale, C. A. & Bawendi, M. G. Quantization of multiparticle Auger rates in semiconductor quantum Dots. Science 287, 1011–1013 (2000).10.1126/science.287.5455.1011 ↗
63. Nirmal, M. et al. Fluorescence intermittency in single cadmium selenide nanocrystals. Nature 383, 802–804 (1996).10.1038/383802a0 ↗
64. Li, B. et al. Excitons and biexciton dynamics in single CsPbBr3 perovskite quantum dots. J. Phys. Chem. Lett. 9, 6934–6940 (2018).10.1021/acs.jpclett.8b03098 ↗
65. Hu, F. et al. Carrier multiplication in a single semiconductor nanocrystal. Phys. Rev. Lett. 116, 106404 (2016).10.1103/PhysRevLett.116.106404 ↗