Construction of electron donor-acceptor(D-A)conjugated system is an established strategy for achieving reverse saturable absorption(RSA)and broadband optical limiting(OL).Nevertheless,organic materials exhibit OL abil...Construction of electron donor-acceptor(D-A)conjugated system is an established strategy for achieving reverse saturable absorption(RSA)and broadband optical limiting(OL).Nevertheless,organic materials exhibit OL ability across the visible to near-infrared-II spectra range remain scarce.Herein,a series of D-A typeπ-conjugated copolymers with ultra-narrow bandgaps(0.62-0.76 e V)and strong ICT absorption were synthesized by coupling electron-withdrawing block[1,2,5]thiadiazolo[3,4-g]quinoxaline(TQ)with various electron-donating groups(thiophene,selenophene,bithiophene,di(thiophen-2-yl)ethene,and thienothiophene for P1-P5,respectively).Z-scan experiments reveal that all copolymers exhibit RSA behaviours at both 532 and 1064 nm,while P1,P3 and P4 maintain RSA performance extending to 1600 nm.Among all copolymers,P5 exhibits the strongest RSA performance upon both 532 and 1064 nm laser pulses,with the highest nonlinear absorption coefficient(β_(eff))of 51.5 and 49.4 cm·GW^(-1),respectively,and the lowest OL onset fluence(Fon)of 0.31 and 0.38 J·cm^(-2),respectively.In contrast,P4 shows optimal RSA property at 1600 nm laser pulse,withβeff of 13.1 cm·GW^(-1)and Fon of 1.43 J·cm^(-2),respectively.Combining the results of Z-scan and UV-Vis-NIR experiments,it can be speculated that moderate ground-state absorption,rather than excessively strong absorption,favors superior RSA properties.This work offers valuable insights for designing copolymers with excellent RSA behavior,as well as presents a class of candidate material systems for ultrabroadband optical limiting.展开更多
基金supported by the National Natural Science Foundation of China(No.52102013)。
文摘Construction of electron donor-acceptor(D-A)conjugated system is an established strategy for achieving reverse saturable absorption(RSA)and broadband optical limiting(OL).Nevertheless,organic materials exhibit OL ability across the visible to near-infrared-II spectra range remain scarce.Herein,a series of D-A typeπ-conjugated copolymers with ultra-narrow bandgaps(0.62-0.76 e V)and strong ICT absorption were synthesized by coupling electron-withdrawing block[1,2,5]thiadiazolo[3,4-g]quinoxaline(TQ)with various electron-donating groups(thiophene,selenophene,bithiophene,di(thiophen-2-yl)ethene,and thienothiophene for P1-P5,respectively).Z-scan experiments reveal that all copolymers exhibit RSA behaviours at both 532 and 1064 nm,while P1,P3 and P4 maintain RSA performance extending to 1600 nm.Among all copolymers,P5 exhibits the strongest RSA performance upon both 532 and 1064 nm laser pulses,with the highest nonlinear absorption coefficient(β_(eff))of 51.5 and 49.4 cm·GW^(-1),respectively,and the lowest OL onset fluence(Fon)of 0.31 and 0.38 J·cm^(-2),respectively.In contrast,P4 shows optimal RSA property at 1600 nm laser pulse,withβeff of 13.1 cm·GW^(-1)and Fon of 1.43 J·cm^(-2),respectively.Combining the results of Z-scan and UV-Vis-NIR experiments,it can be speculated that moderate ground-state absorption,rather than excessively strong absorption,favors superior RSA properties.This work offers valuable insights for designing copolymers with excellent RSA behavior,as well as presents a class of candidate material systems for ultrabroadband optical limiting.
