Circularly polarized laser from three-dimensional perovskite induced by intramolecular interaction

Abstract

Materials with circularly polarized (CP) lasing, featuring optical rotatory power, are attractive for various advanced optical, sensing, biological, and medical applications. In this context, chiral perovskites attract great attention owing to their superior chiral opto-electronic-magnetic properties. However, the trade-off between coherence and circularity hinders lasing in low-dimensional perovskites. Herein, we invent a novel strategy to realize three-dimensional perovskites with high chirality featuring CP laser. The strong intramolecular interaction between chiral acid and inorganic framework via ionic bonding leads to intense electronic interaction and orbital hybridization, resulting in higher asymmetric and efficient CP emission than most low-dimensional perovskites and an amplified asymmetric factor of up to 0.054 at up-threshold excitation. This pioneering advancement heralds a new era for intramolecular interaction-based stable perovskite, as well as other low-dimensional materials, opening avenues for unprecedented applications in stable-perovskite/chiral optoelectronics and beyond.

Keywords

3D metal halide perovskite / chirality transfer / circularly polarized lasers / continuous wave / ionic/covalent bonding

References

[1] Deng Y, Wang M, Zhuang Y, Liu S, Huang W, Zhao Q. Circularly polarized luminescence from organic micro-/nano-structures. Light Sci Appl. 2021;10(1):76.

[2] Barik S, Karasahin A, Flower C, et al. A topological quantum optics interface. Science. 2018;359(6376):666-668.

[3] Zhang Y, Yu S, Han B, et al. Circularly polarized luminescence in chiral materials. Matter. 2022;5(3):837-875.

[4] Feng L-Z, Wang JJ, Ma T, et al. Biomimetic non-classical crystallization drives hierarchical structuring of efficient circularly polarized phosphors. Nat Commun. 2022;13(1):3339.

[5] Stachelek P, MacKenzie L, Parker D, Pal R. Circularly polarised luminescence laser scanning confocal microscopy to study live cell chiral molecular interactions. Nat Commun. 2022;13(1):553.

[6] Zhan X, Xu FF, Zhou Z, Yan Y, Yao J, Zhao YS. 3D laser displays based on circularly polarized lasing from cholesteric liquid crystal arrays. Adv Mater. 2021;33(37):e2104418.

[7] Zhang M, Guo Q, Li Z, et al. Processable circularly polarized luminescence material enables flexible stereoscopic 3D imaging. Sci Adv. 2023;9(43):eadi9944.

[8] Baek K, Lee DM, Lee YJ, et al. Simultaneous emission of orthogonal handedness in circular polarization from a single luminophore. Light Sci Appl. 2019;8(1):120.

[9] Chen Y, Du W, Zhang Q, et al. Multidimensional nanoscopic chiroptics. Nat Rev Phys. 2021;4(2):113-124.

[10] Dong Y, Zhang Y, Li X, Feng Y, Zhang H, Xu J. Chiral perovskites: promising materials toward next-generation optoelectronics. Small. 2019;15(39):e1902237.

[11] Long G, Sabatini R, Saidaminov MI, et al. Chiral-perovskite optoelectronics. Nat Rev Mater. 2020;5(6):423-439.

[12] Kim Y-H, Zhai Y, Lu H, et al. Chiral-induced spin selectivity enables a room-temperature spin light-emitting diode. Science. 2021;371(6534):1129-1133.

[13] Long G, Jiang C, Sabatini R, et al. Spin control in reduced-dimensional chiral perovskites. Nat Photonics. 2018;12(9):528-533.

[14] Yang CK, Chen WN, Ding YT, et al. The first 2D homochiral lead iodide perovskite ferroelectrics: [R- and S-1-(4-chlorophenyl) ethylammonium]₂PbI₄. Adv Mater. 2019;31(16):1808088.

[15] Li L, Shang X, Wang S, et al. Bilayered hybrid perovskite ferroelectric with giant two-photon absorption. J Am Chem Soc. 2018;140(22):6806-6809.

[16] Fu D, Xin J, He Y, Wu S, Zhang X, Luo J. Chirality-dependent second-order nonlinear optical effect in 1D organic–inorganic hybrid perovskite bulk single crystal. Angew Chem Int Ed Engl. 2021;60(36):20021-20026.

[17] Li J, Guo Z, Wang M, et al. Regulating second-harmonic generation in 2D chiral perovskites through achiral organic spacer cation alloying strategy. Laser Photon Rev. 2025;19(4):2401379.

[18] Guo Z, Li J, Liu R, et al. Spatially correlated chirality in chiral two-dimensional perovskites revealed by second-harmonic-generation circular dichroism microscopy. Nano Lett. 2023;23(16):7434-7441.

[19] Smith MD, Connor BA, Karunadasa HI. Tuning the luminescence of layered halide perovskites. Chem Rev. 2019;119(5):3104-3139.

[20] Yuan S, Dai L, Sun Y, et al. Efficient blue electroluminescence from reduced-dimensional perovskites. Nat Photonics. 2024;18(5):425-431.

[21] Park JY, Song R, Liang J, et al. Thickness control of organic semiconductor-incorporated perovskites. Nat Chem. 2023;15(12):1745-1753.

[22] Li Y, Zhou H, Xia M, et al. Phase-pure 2D tin halide perovskite thin flakes for stable lasing. Sci Adv. 2023;9(32): eadh0517.

[23] Wang X, Jin L, Sergeev A, et al. Quasi-2D Dion-Jacobson phase perovskites as a promising material platform for stable and high-performance lasers. Sci Adv. 2023;9(43):eadj3476.

[24] Ma S, Jung YK, Ahn J, et al. Elucidating the origin of chiroptical activity in chiral 2D perovskites through nano-confined growth. Nat Commun. 2022;13(1):3259.

[25] Tohgha U, Deol KK, Porter AG, et al. Ligand induced circular dichroism and circularly polarized luminescence in CdSe quantum dots. ACS Nano. 2013;7(12):11094-11102.

[26] Ben-Moshe A, Govorov AO, Markovich G. Enantioselective synthesis of intrinsically chiral mercury sulfide nanocrystals. Angew Chem Int Ed. 2013;52(4):1275-1279.

[27] Long G, Zhou Y, Zhang M, et al. Theoretical prediction of chiral 3D hybrid organic–inorganic perovskites. Adv Mater. 2019;31(17): e1807628.

[28] Huang S, Huang P, Wang L, Han J, Chen Y, Zhong H. Halogenated-methylammonium based 3D halide perovskites. Adv Mater. 2019;31(42):1903830.

[29] Zhang Z, Qiao L, Meng K, Long R, Chen G, Gao P. Rationalization of passivation strategies toward high-performance perovskite solar cells. Chem Soc Rev. 2023;52(1):163-195.

[30] Chen B, Rudd PN, Yang S, Yuan Y, Huang J. Imperfections and their passivation in halide perovskite solar cells. Chem Soc Rev. 2019;48(14):3842-3867.

[31] Man T, Gong N, Li Z, et al. In situ passivation of two-dimensional perovskites by external electric field. Adv Opt Mater. 2023;11(23):2300969.

[32] Zhang Y, Sun M, Zhou N, Huang B, Zhou H. Electronic tunability and mobility anisotropy of quasi-2D perovskite single crystals with varied spacer cations. J Phys Chem Lett. 2020;11(18):7610-7616.

[33] Ban M, Zou Y, Rivett JPH, et al. Solution-processed perovskite light emitting diodes with efficiency exceeding 15% through additive-controlled nanostructure tailoring. Nat Commun. 2018;9(1):3892.

[34] Zhang Z, Gao Y, Li Z, et al. Marked passivation effect of naphthalene-1,8-dicarboximides in high-performance perovskite solar cells. Adv Mater. 2021;33(31):2008405.

[35] Cho H, Jeong SH, Park MH, et al. Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes. Science. 2015;350(6265):1222-1225.

[36] Ma D, Lin K, Dong Y, et al. Distribution control enables efficient reduced-dimensional perovskite LEDs. Nature. 2021;599(7886):594-598.

[37] Han D, Wang J, Agosta L, et al. Tautomeric mixture coordination enables efficient lead-free perovskite LEDs. Nature. 2023;622(7983):493-498.

[38] Zhu L, Cao H, Xue C, et al. Unveiling the additive-assisted oriented growth of perovskite crystallite for high performance light-emitting diodes. Nat Commun. 2021;12(1):5081.

[39] Huang Z, Bai Y, Huang X, et al. Anion–π interactions suppress phase impurities in FAPbI₃ solar cells. Nature. 2023;623(7987):531-537.

[40] Li F, Deng X, Shi Z, et al. Hydrogen-bond-bridged intermediate for perovskite solar cells with enhanced efficiency and stability. Nat Photonics. 2023;17(6):478-484.

[41] Jiao H, Ni Z, Shi Z, et al. Perovskite grain wrapping by converting interfaces and grain boundaries into robust and water-insoluble low-dimensional perovskites. Sci Adv. 2022;8:4524.

[42] Gu L, Ye W, Liang X, et al. Circularly polarized organic room temperature phosphorescence from amorphous copolymers. J Am Chem Soc. 2021;143(44):18527-18535.

[43] Lu H, Vardeny ZV, Beard MC. Control of light, spin and charge with chiral metal halide semiconductors. Nat Rev Chem. 2022;6(7):470-485.

[44] Fiuza-Maneiro N, Sun K, López-Fernández I, Gómez-Graña S, Müller-Buschbaum P, Polavarapu L. Ligand chemistry of inorganic lead halide perovskite nanocrystals. ACS Energy Lett. 2023;8(2):1152-1191.

[45] Guo J, Liu T, Li M, et al. Ultrashort laser pulse doubling by metal-halide perovskite multiple quantum wells. Nat Commun. 2020;11(1):3361.

[46] Wu Y, Xu J, Poh ET, et al. Upconversion superburst with sub-2 μs lifetime. Nat Nanotechnol. 2019;14(12):1110-1115.

[47] Yang S, Bao W, Liu X, et al. Subwavelength-scale lasing perovskite with ultrahigh Purcell enhancement. Matter. 2021;4(12):4042-4050.

[48] Liu X, Wang K, Zhang T, et al. Exciton chirality transfer empowers self-triggered spin-polarized amplified spontaneous emission from 1D-anchoring-3D perovskites. Adv Mater. 2023;35(52):e2305260.

[49] Lin W, Yang C, Miao Y, et al. Toward chiral lasing from all-solution-processed flexible perovskite-nanocrystal–liquid-crystal membranes. Adv Mater. 2023;35(44):2301573.

[50] Yuan Z, Zhou Y, Qiao Z, et al. Stimulated chiral light-matter interactions in biological microlasers. ACS Nano. 2021;15(5):8965-8975.

[51] Wu T, Wang Y, Li X, et al. Efficient defect passivation for perovskite solar cells by controlling the electron density distribution of donor-π-acceptor molecules. Adv Energy Mater. 2019;9(17):1803766.

[52] Shen W, Cai H, Kong Y, et al. Protic amine carboxylic acid ionic liquids additives regulate α-FAPbI₃ phase transition for high efficiency perovskite solar cells. Small. 2023;19(36):2302194.

[53] Zhang H, Pfeifer L, Zakeeruddin SM, Chu J, Grätzel M. Tailoring passivators for highly efficient and stable perovskite solar cells. Nat Rev Chem. 2023;7(9):632-652.

[54] Han TH, Lee JW, Choi C, et al. Perovskite-polymer composite cross-linker approach for highly-stable and efficient perovskite solar cells. Nat Commun. 2019;10(1):520.

[55] Bi D, Yi C, Luo J, et al. Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%. Nat Energy. 2016;1(10):16142.

[56] Chen X, Lu H, Wang K, et al. Tuning spin-polarized lifetime in two-dimensional metal-halide perovskite through exciton binding energy. J Am Chem Soc. 2021;143(46):19438-19445.

[57] Yao J, Wang Z, Huang Y, et al. Efficient green spin light-emitting diodes enabled by ultrafast energy- and spin-funneling in chiral perovskites. J Am Chem Soc. 2024;146(20):14157-14165.

[58] Chen S, Zhang C, Lee J, Han J, Nurmikko A. High-Q, low-threshold monolithic perovskite thin-film vertical-cavity lasers. Adv Mater. 2017;29:1604781.

RIGHTS & PERMISSIONS

2025 The Author(s). InfoMat published by UESTC and John Wiley & Sons Australia, Ltd.