Lead-based perovskite nanocrystals (NCs) have outstanding optical properties and cheap synthesis conferring them a tremendous potential in the field of optoelectronic devices. However, two critical problems are still unresolved and hindering their commercial applications: one is the fact of being lead-based and the other is the poor stability. Lead-free all-inorganic perovskite Cs Bi X (X=Cl, Br, I) NCs are synthesized with emission wavelength ranging from 400 to 560 nm synthesized by a facile room temperature reaction. The ligand-free Cs Bi Br NCs exhibit blue emission with photoluminescence quantum efficiency (PLQE) about 0.2 %. The PLQE can be increased to 4.5 % when extra surfactant (oleic acid) is added during the synthesis processes. This improvement stems from passivation of the fast trapping process (2-20 ps). Notably, the trap states can also be passivated under humid conditions, and the NCs exhibited high stability towards air exposure exceeding 30 days.
Lead-free double-perovskite nanocrystals (NCs), that is, Cs2AgIn x Bi1–x Cl6 (x = 0, 0.25, 0.5, 0.75, and 0.9), that can be tuned from indirect band gap (x = 0, 0.25, and 0.5) to direct band gap (x = 0.75 and 0.9) are designed. Direct band gap NCs exhibit 3 times greater absorption cross section, lower sub-band gap trap states, and >5 times photoluminescence quantum efficiency (PLQE) compared to those observed for indirect band gap NCs (Cs2AgBiCl6). A PLQE of 36.6% for direct band gap NCs is comparable to those observed for lead perovskite NCs in the violet region. Besides the band edge violet emission, the direct band gap NCs exhibit bright orange (570 nm) emission. Density functional theory calculations suggesting forbidden transition is responsible for the orange emission, which is supported by time-resolved PL and PL excitation spectra. The successful design of lead-free direct band gap perovskite NCs with superior optical properties opens the door for high-performance lead-free perovskite optoelectronic devices.
Lead-free perovskite nanocrystals (NCs) were obtained mainly by substituting a Pb cation with a divalent cation or substituting three Pb cations with two trivalent cations. The substitution of two Pb cations with one monovalent Ag and one trivalent Bi cations was used to synthesize Cs AgBiX (X=Cl, Br, I) double perovskite NCs. Using femtosecond transient absorption spectroscopy, the charge carrier relaxation mechanism was elucidated in the double perovskite NCs. The Cs AgBiBr NCs exhibit ultrafast hot-carrier cooling (<1 ps), which competes with the carrier trapping processes (mainly originate from the surface defects). Notably, the photoluminescence can be increased by 100 times with surfactant (oleic acid) added to passivate the defects in Cs AgBiCl NCs. These results suggest that the double perovskite NCs could be potential materials for optoelectronic applications by better controlling the surface defects.
Low trap-state density, high carrier mobility, and efficient charge carrier collection are key parameters for photodetectors with high sensitivity and fast response time. This study demonstrates a simple solution growth method to prepare CsPbBr microcrystals (MCs) with low trap-state density. Time-dependent photoluminescence study with one-photon excitation (OPE) and two-photon excitation (TPE) indicates that CsPbBr MCs exhibit fast carrier diffusion with carrier mobility over 100 cm V S . Furthermore, CsPbBr MC-based photodetectors with high charge carriers' collection efficiency are fabricated. Such photodetectors show ultrahigh responsivity (R) up to 6 × 10 A W with OPE and high R up to 6 A W with TPE. The R for OPE is over one order of magnitude higher (the R for TPE is three orders of magnitude higher) than that of previously reported all-inorganic perovskite-based photodetectors. Moreover, the photodetectors exhibit fast response time of ≈1 ms, which corresponds to a gain ≈10 and a gain- bandwidth product of 10 Hz for OPE (a gain ≈10 and a gain-bandwidth product of 10 Hz for TPE).
Lead‐free halide perovskite nanocrystals (NCs) have drawn wide attention for solving the problem of lead perovskites toxicity and instability. Herein, we synthesize the direct band gap double perovskites undoped and Ag‐doped Cs2NaInCl6 NCs by variable temperature hot injection. The Cs2NaInCl6 NCs have little photoluminescence because of dark self‐trapped excitons (STEs). The dark STEs can be converted into bright STEs by doping with Ag+ to produce a bright yellow emission, with the highest photoluminescence quantum efficiency of 31.1 %. The dark STEs has been directly detected experimentally by ultrafast transient absorption (TA) techniques. The dynamics mechanism is further studied. In addition, the Ag‐doped NCs show better stability than the undoped ones. This result provides a new way to enhance the optical properties of lead‐free perovskites NCs for high‐performance light emitters.
Lead‐free perovskite nanocrystals (NCs) were obtained mainly by substituting a Pb2+ cation with a divalent cation or substituting three Pb2+ cations with two trivalent cations. The substitution of two Pb2+ cations with one monovalent Ag+ and one trivalent Bi3+ cations was used to synthesize Cs2AgBiX6 (X=Cl, Br, I) double perovskite NCs. Using femtosecond transient absorption spectroscopy, the charge carrier relaxation mechanism was elucidated in the double perovskite NCs. The Cs2AgBiBr6 NCs exhibit ultrafast hot‐carrier cooling (<1 ps), which competes with the carrier trapping processes (mainly originate from the surface defects). Notably, the photoluminescence can be increased by 100 times with surfactant (oleic acid) added to passivate the defects in Cs2AgBiCl6 NCs. These results suggest that the double perovskite NCs could be potential materials for optoelectronic applications by better controlling the surface defects.
Thermally activated delayed fluorescence (TADF) is generally observed in solid-state organic molecules or metalorganic complexes. However, TADF in all-inorganic colloidal nanocrystals (NCs) is rare. Herein, we report the first colloidal synthesis of an air-stable all-inorganic lead-free Cs 2 ZrCl 6 perovskite NCs. The Cs 2 ZrCl 6 NCs exhibit long-lived triplet excited state (138.2 ms), and feature high photoluminescence (PL) quantum efficiency (QY = 60.37 %) due to TADF mechanism. The emission color can be easily tuned from blue to green by synthesizing the mixed-halide Cs 2 ZrBr x Cl 6Àx (0 x 1.5) NCs. Femtosecond transient absorption and temperature dependent PL measurements are performed to clarify the emission mechanism. In addition, Bi 3+ ions are successfully doped into Cs 2 ZrCl 6 NCs, which further extends the PL properties. This work not only develops a new lead-free halide perovskite NCs for potential optoelectronic applications, but also offers unique strategies for developing new inorganic phosphors.
Conspectus Lead halide perovskite nanocrystals (NCs) have been widely studied for application in optoelectronic devices due to their excellent optical properties and low-cost synthesis. However, the toxicity of lead and the poor stability of the NCs hindered their practical applications. Sn2+-based perovskite with low toxicity was first developed; however, the Sn2+-based perovskite NCs are unstable in air and oxidize easily. Recently, air-stable lead-free perovskite NCs have been developed and received increasing attention. Unfortunately, the optical and optoelectronic properties of these lead-free halide perovskite NCs are generally far worse than those of lead-perovskite NCs. Understanding the charge-carrier dynamics of semiconductors is crucial to improve their optical properties. In this Account, we mainly review our recent research progress on the study of charge-carrier dynamics in air-stable lead-free perovskite NCs. The exciton trapping followed by nonradiative recombination was the major carrier relaxation pathway and resulted in a low photoluminescence quantum efficiency (PLQE). A feasible route for passivating surface traps and tuning the self-trapped excitons from “dark” (nonradiative) to “bright” (radiative) was proposed. Through this strategy, the PLQE could be increased over 100-fold. In addition, we have compared several photophysical properties of lead-free perovskite NCs with that of lead perovskite NCs, such as charge-carrier relaxation, exciton–phonon coupling, and hot-carrier cooling. In 2017, we reported the synthesis, optical properties, and charge-carrier dynamics of Cs3Bi2X9 (X: Cl, Br, I) NCs. The Cs3Bi2Br9 NCs exhibited clear exciton trapping processes with time scales in the range of 2–20 ps. The fast trapping processes could be passivated via the use of surfactants (such as oleic acid), and the PLQE increased over 20-fold (from 0.2% to 4.5%). The low PLQE may be due to the reduced dimensionality of Cs3Bi2Br9 (2D) compared with the 3D cubic perovskite structure of CsPbBr3. We next reported double perovskite Cs2AgSb1–y Bi y X6 (X: Br, Cl; 0 ≤ y ≤ 1) NCs, which exhibited a similar 3D cubic perovskite structure to that of the lead-perovskite NCs. The charge-carrier dynamics indicated that the sub-band-gap exciton trapping processes were dominated by ultrafast (∼1–2 ps) intrinsic self-trapping and trapping at surface defects (∼50–100 ps). While trapping at surface defects can be passivated using surfactants, the self-trapping processes is due to the giant carrier–phonon coupling effect. By designing direct band gap double perovskite NCs to tune the sub-band-gap trapping processes, bright dual-color emission was achieved. Furthermore, the violet PLQE could be improved to 36.6%, which is comparable to that in lead halide perovskite NCs. We hope this Account will deepen the understanding of the charge-carrier dynamics in lead-free perovskite NCs and guide the design of high-performance lead-free perovskites.
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