All‐inorganic bismuth‐halide perovskites are promising alternatives for lead halide perovskites due to their admirable chemical stability and optoelectronic properties; however, these materials deliver inferior photoluminescence (PL) properties, severely hindering their prospects in lighting applications. Here, a novel air‐stable but non‐emissive perovskite Rb3BiCl6 is synthesized, and the material is used as a prototype to uncover origin of the poor optical performance in bismuth‐halide perovskite. It is found that the extremely strong exciton–phonon interactions with a large coupling constant up to 693 meV leads to the seriously nonradiative recombination, which, however, can be effectively suppressed to 347 meV by introducing Sb3+ ions. As a result, Sb3+‐doped Rb3BiCl6 exhibits a stable yellow emission with unprecedented PL quantum yield up to 33.6% from self‐trapped excitons. Systematic spectroscopic characterizations and theoretical calculations are carried out to unveil the intriguing photophysical mechanisms. This work reveals the effect of exciton–phonon interaction, that is often underemphasized, on a material's photophysical properties.

We present an effective strategy to modulate the electron-rich capability in donor–acceptor (D-A) polymers for improving the performances of organic solar cell (OSC) devices. In order to confirm this strategy, based on a series of the reported D–A polymers ((PCPDTBT(Pa1), PCPDTFBT (Pa2), and PCPDTDFBT (Pa3)) which contain the electron-donating cyclopentadithiophene (CPDT) and differently electron-withdrawing units of benzo[c][1,2,5,]thiadiazole (BT), 5-fluorobenzo[c][1,2,5]thiadiazole (FBT), and 5,6-difluorobenzo[c] [1,2,5]thiadiazole (DFBT), we replace CPDT with electron-donating dithienogermolodithiophene (DTTG) in polymers Pa1–Pa3, respectively, and design a series of new D–A polymers Pb1–Pb3. Compared with the polymers Pa1–Pa3, the new designed polymers Pb1–Pb3 not only yield a greater red-shift of the absorption spectrum of the donor polymer and result in a larger absorption region within the solar emission spectrum and an improved light-absorbing efficiency but also exhibit much better electron transfer efficiency in active layer, larger hole transport rates and higher open circuit voltage. Moreover, the estimated power conversion efficiency of the designed polymers in OSC applications reaches up to ∼8.4%. Conclusively, the approach based on modulating the electron-donating capability in D–A polymer chain is a feasible way to enhance their intrinsic properties of donor polymers and thereby achieving the purpose that improves the performances of the OSC devices.

Because of the good thermal stability and superior carrier transport characteristics of formamidinium lead trihalide perovskite HC(NH2)2PbX3 (FAPbX3), it has been considered to be a better optoelectronic material than conventional CH3NH3PbX3 (MAPbX3). Herein, we fabricated a FAPbBr3 microcrystal-based photodetector that exhibited a good responsivity of 4000 A W−1 and external quantum efficiency up to 106% under one-photon excitation, corresponding to the detectivity greater than 1014 Jones. The responsivity is two orders of magnitude higher than that of previously reported formamidinium perovskite photodetectors. Furthermore, the FAPbBr3 photodetector’s responsivity to two-photon absorption with an 800-nm excitation source can reach 0.07 A W−1, which is four orders of magnitude higher than that of its MAPbBr3 counterparts. The response time of this photodetector is less than 1 ms. This study provides solid evidence that FAPbBr3 can be an excellent candidate for highly sensitive and fast photodetectors.Electronic supplementary materialThe online version of this article (10.1007/s40820-018-0196-2) contains supplementary material, which is available to authorized users.

No abstract

Tin(IV)-based metal halides are promising optoelectronic materials due to their robust structure and eco-friendly nature, but these materials exhibit poor photoluminescence (PL) properties and the underlying mechanisms are still elusive. Here, a novel air-stable hybrid Sn 4+ -halide material (C 8 H 22 N 2 Cl) 2 SnCl 6 that is resistant to moisture (>70% relative humidity) for >1 year is reported. The inferior PL property of (C 8 H 22 N 2 Cl) 2 SnCl 6 is limited by the lattice defects and robust crystal structure, which however could be effectively improved by introducing Sb 3+ ion with stereoactive 5s 2 lone pair. As a result, Sb 3+doped (C 8 H 22 N 2 Cl) 2 SnCl 6 exhibits a superbly stable room-temperature PL centered at 690 nm with an unprecedented quantum yield (QY) of 41.76% from self-trapped excitons, which is the highest PLQY of hybrid tin(IV)-based perovskite materials. The improved PL efficiency is attributed to the defect passivation and remarkable structure distortion induced by Sb 3+ dopants. This dopant-induced defect passivation and exciton self-trapping approach offers an avenue to improve optoelectronic material performance.

A mass of porphyrin sensitizers have been designed and synthesized for dye-sensitized solar cells in previous works, and almost all of them incorporated an electron-rich system as the π-spacer. We here adopted the electron-deficient pyrimidine as an effective π-spacer and combined a cyanoacrylic acid anchoring group, as such a design yields a more bathochromic shift of the spectral absorption of the dye and results in an improved spectral overlap with the solar spectrum and an enhanced light-harvesting efficiency. The result does tally with the performance of sensitizer adsorbing on a semiconductor. From the electron density difference plots of electron transitions, we found that not all electron transitions could make for the effective electron transfer from donor to acceptor groups, which means the sensitizer performance in dye-sensitized solar cells not only relies on the extrinsic spectral absorption intensity but also depends on the intrinsic character of electron movement related to electron excitation. Moreover, the introduction of electron-deficient pyrimidine could affect the energy levels of excited molecules in solution, further affecting the kinds of electron transfer processes. We presented several novel porphyrin sensitizers for comparison on how the π-spacer and anchoring group influence the optical absorption, electron transfer processes, and regeneration of the oxidized dyes, thereby gaining potential dye-sensitized solar cells with highly efficient photo-to-electric conversion performances.

Both trap-state densities and energy levels affect carrier transfer, resulting in a maximum diffusion length of 380 μm in CH3NH3PbI3−xClx (x = 0.005).

No abstract