Light-induced halide segregation limits the bandgap tunability of mixed-halide perovskites for tandem photovoltaics. Here we report that light-induced halide segregation is strain-activated in MAPb(I1−xBrx)3 with Br concentration below approximately 50%, while it is intrinsic for Br concentration over approximately 50%. Free-standing single crystals of CH3NH3Pb(I0.65Br0.35)3 (35%Br) do not show halide segregation until uniaxial pressure is applied. Besides, 35%Br single crystals grown on lattice-mismatched substrates (e.g. single-crystal CaF2) show inhomogeneous segregation due to heterogenous strain distribution. Through scanning probe microscopy, the above findings are successfully translated to polycrystalline thin films. For 35%Br thin films, halide segregation selectively occurs at grain boundaries due to localized strain at the boundaries; yet for 65%Br films, halide segregation occurs in the whole layer. We close by demonstrating that only the strain-activated halide segregation (35%Br/45%Br thin films) could be suppressed if the strain is properly released via additives (e.g. KI) or ideal substrates (e.g. SiO2).
Predictive knowledge of ion transport in electrolytes which bridges microscopic and macroscopic length scales is imperative to design new ion conductors and to simulate device performance. Here, we employed a...
Metal-halide-perovskites revolutionized the field of thin-film semiconductor technology, due to their favorable optoelectronic properties and facile solution processing. Further improvements of perovskite thin-film devices require structural coherence on the atomic scale. Such perfection is achieved by epitaxial growth, a method that is based on the use of high-end deposition chambers. Here epitaxial growth is enabled via a ≈1000 times cheaper device, a single nozzle inkjet printer. By printing, single-crystal micro-and nanostructure arrays and crystalline coherent thin films are obtained on selected substrates. The hetero-epitaxial structures of methylammonium PbBr 3 grown on lattice matching substrates exhibit similar luminescence as bulk single crystals, but the crystals phase transitions are shifted to lower temperatures, indicating a structural stabilization due to interfacial lattice anchoring by the substrates. Thus, the inkjet-printing of metal-halide perovskites provides improved material characteristics in a highly economical way, as a future cheap competitor to the high-end semiconductor growth technologies.
Summary
Here, we evaluate three different noble metal co-catalysts (Pd, Pt, and Au) that are present as single atoms (SAs) on the classic benchmark photocatalyst, TiO
2
. To trap the single atoms on the surface, we introduced controlled surface vacancies (Ti
3+
-O
v
) on anatase TiO
2
nanosheets by a thermal reduction treatment. After anchoring identical loadings of single atoms of Pd, Pt, and Au, we measure the photocatalytic H
2
generation rate and compare it to the classic nanoparticle co-catalysts on the nanosheets. While nanoparticles yield the well-established the hydrogen evolution reaction activity sequence (Pt > Pd > Au), for the single atom form, Pd radically outperforms Pt and Au. Based on density functional theory (DFT), we ascribe this unusual photocatalytic co-catalyst sequence to the nature of the charge localization on the noble metal SAs embedded in the TiO
2
surface.
The use of single atoms (SAs) has become a highly investigated topic in heterogeneous catalysis, electrocatalysis, and most recently also in photocatalysis. In the field of photocatalysis, Pt SAs on TiO2 have been reported to be a highly efficient co‐catalyst in solar H2 production. Herein, the deposition of Pt SAs and nanoparticles on titania nanosheets is investigated. In particular, the Pt species responsible for the high co‐catalytic activity using a cyanide leaching process is elucidated. It is shown that neither Pt0 species nor the majority of Pt SAs do significantly contribute to the co‐catalytic activity of platinum on TiO2. In fact, >90% of the Pt of a standard deposition are non‐active and can be removed by cyanide leaching without activity loss—as a consequence, the remaining Pt SAs amount to a remarkable turnover frequency of 4.87 × 105 h−1 for H2 evolution.
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