A mild aqueous synthesis of colloidal 2−4 nm (Cu, Ag)− In−S (CAIS) quantum dots (QDs) stabilized by surface metal complexes with glutathione was introduced. Linear variations of the interplanar distances as well as of the characteristic Ag(Cu)−S-related Raman vibrational frequencies of CAIS QDs with the increasing copper content show such QDs to be solid solutions rather than a mixture of AIS and CIS phases. At the same time, the band gaps and the energies of the photoluminescence (PL) band maxima of CAIS QDs show nonmonotonous changes decreasing from AIS to CAIS QDs (50 mol % Cu) and then increasing back for Cu-richer CAIS compositions and pure CIS. This behavior was interpreted as a result of the band bowing phenomenon. The bowing parameters of CAIS QDs determined from both absorption spectra (1.10 eV) and PL spectra (0.38 eV) are close to the range typically reported for ternary bulk M I −M III −S compounds with the M I sites occupied by a mixture of copper and silver cations. The PL intensity of CAIS QDs was found to decrease during PL registration due to the photochemical decomposition of QDs, and the efficiency of this process increases with the increasing copper content. A similar trend was found in the photocatalytic reduction of methylviologen cations by hydrosulfide anions in the presence of CAIS. The initial rate of this reaction increased monotonously from AIS to CAIS to CIS QDs, with the activity of the CAIS QDs (50 mol % Cu) and pure CIS QDs being, respectively, 1.5 and 2.7 times higher than the photoactivity of pure AIS QDs. This trend is compliant with a strong decrease in the PL emission efficiency observed from AIS to CAIS to CIS QDs. Similar optical and photochemical properties were revealed for core/shell CAIS/ZnS QDs. The band bowing effect and photochemical activity of mixed CAIS (CAIS/ZnS) QDs open good perspectives for light-conversion applications in the photon energy range down to 1.8 eV.
Lead−Tin perovskite solar cells (Pb/Sn PSCs) are limited by the intrinsic instability of Sn(II), which tends to oxidize forming Sn vacancies in perovskite films. Herein, a Lewis base β-guanidinopropionic acid (GUA) and hydrazinium iodide (HAI) are introduced to effectively passivate the perovskite bulk and surface, respectively. The synergistic approach leads to Pb/Sn PSCs with a promising power conversion efficiency of 20.5% owing to the significantly reduced nonradiative recombination and voltage losses. As a result, the V OC × FF product of PSCs is significantly improved, which is among the highest values documented in the literature, being favorable for perovskite-based tandem applications. Additionally, the strategy demonstrated in this work could also improve the stability of PSCs by enhancing the chemical robustness of the perovskite layer. These results emphasize the significance of bulk and surface passivation in the development of efficient and stable PSCs based on Pb/Sn perovskites.
Microcrystalline Cs2AgxNa1−xBiyIn1−yCl6 perovskites with tailored composition emitting broadband yellow-white photoluminescence with a quantum yield of up to 92% were produced by a new “green” approach under ambient conditions.
A new single-step and green approach for the synthesis of microcrystalline Cs2AgxNa1-xBiyIn1-yCl6 (CANBIC) perovskites in ambient conditions is introduced. The CANBIC powders emit broadband yellow-white self-trapped excitonic photoluminescence (PL) with...
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