Effect of Mn2+ Doping on the Photoluminescence of Hybrid One-Dimensional Lead Halide Post-Perovskites.

Although organic-inorganic hybrid one-dimensional (1D) lead halide postperovskites (LHPPs) have been reported to show white luminescence and tunable photoluminescence quantum yield (PLQY), their structure-property relationships are not fully understood. Here, we used Mn2+ to test the doping effect on the luminescence of two 1D-LHPPs compounds, namely, {TETA[Pb2Br6]}n 1 and {TETA[Pb2Cl6]}n 2, where TETA = triethylenetetrammonium. We found the pristine compounds show yellowish (551 nm) and bluish (447 nm) emission for 1 and 2, respectively, nanosecond excitation lifetimes (4.17 ns for 1 and 2.29 ns for 2) and low PLQYs (4.65 and 3.57% for 1 and 2, respectively). By fine-doping the Mn2+ ions to ca. 8% the PLQYs for 1 and 2 are maximized to 24 and 25% for 1 and 2, respectively. Upon the increasing Mn2+ dopant, the emission wavelengths can also vary gradually from 551 to 615 nm and from 447 to 660 nm for 1 and 2, respectively, covering almost the whole visible-light range, and the excitation lifetimes are enhanced to microseconds (0.77 µs for 1 and 0.39 µs for 2), owing to the more spin-forbidden d-d transition (4T1-6A1) component from the Mn2+ ions present in the photoluminescence spectra. Moreover, these Mn2+-doped 1D-LHPPs demonstrate high structural and optical stability in humid and high-temperature environments. Hence, such doped materials can be fabricated into a UV-pumped white light-emitting diode, rendering the potential application for solid-state lighting and display systems.

Fine Tuning Ag(I)-Sb(III) Hybrid Iodides for Light Detection.

Lead-free hybrid double perovskite iodides (HDPIs) have piqued increasing research interest due to their environmental friendliness and high stability. However, such antimony-based HDPIs with strong photocurrent response are currently very limited. Here, we successfully design and construct five Ag(I)-Sb(III)-based HDPIs using two types of cyclic aliphatic amines as A-site templates. Interestingly, these Ag(I)-Sb(III) HDPIs exhibit relatively narrow band gaps, preferred orientation, and high stability after being processed into thin films on the indium tin oxide (ITO) substrate. Notably, under illuminations of a xenon lamp, all HDPIs exhibit considerable photocurrent responses, reaching a maximum difference of 17 µA·cm-2 for ASI 1, which is the highest among lead-free halogen-based organic-inorganic hybrid compounds to date. Combining the considerable photocurrents and the high stability, the optoelectronic applications of two-dimensional Ag(I)-Sb(III) HDPIs can be expected.

Two-dimensional semiconducting Cu(I)/Sb(III) bimetallic hybrid iodides with a double perovskite structure and photocurrent response.

Stable lead-free hybrid halide double perovskites have sparked widespread interest as a new kind of photoelectric material. Herein, for the first time, we successfully incorporated copper(I) and antimony(III) into two two-dimensional (2D) hybrid bimetallic double perovskite iodides, namely (NH3C6H11)4CuSbI8·H2O (CuSbI-1) and (NH3C6H10NH3)2CuSbI8·0.5H2O (CuSbI-2), using cyclohexylamine and 1,4-cyclohexanediamine as organic components. The band gaps for CuSbI-1 and CuSbI-2 were determined to be 2.22(2) eV and 2.21(2) eV, respectively. Furthermore, these two layered perovskites were readily dissolved in an organic solvent (1 mL DMF can dissolve 1 g sample for each compound) and could form smooth, pinhole-free, and uniform thin films through a facile spin-coating method. Photocurrent experiments with xenon lamp irradiation revealed the obvious photoelectric responses for both 2D double perovskites. The ratio of the photocurrent to the dark current (Ilight/Idark) for CuSbI-1 and CuSbI-2 is about 23 and 10, respectively, further suggesting their potential to be applied as light harvesters or light detectors. More importantly, these 2D double perovskite iodides show high moisture and thermal stabilities, indicating their potential for optoelectronic applications.