Mixed halide hybrid perovskites, CH3NH3Pb(I1−xBrx)3, represent good candidates for low-cost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodide-rich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.
Mixed halide lead perovskites (e.g., CH 3 NH 3 PbBr x I 3−x ) undergo phase segregation creating iodide-rich and bromide-rich domains when subjected to visible irradiation. This intriguing aspect of halide ion movement in mixed halide films is now being tracked through excited-state behavior using emission and transient absorption spectroscopy tools. These transient experiments have allowed us to establish the time scale with which such separation occurs under laser irradiation (405 nm, 25 mW/cm 2 to 1.7 W/cm 2 ) as well as dark recovery. While the phase separation occurs with a rate constant of 0.1−0.3 s −1 , the recovery occurs over a time period of several minutes to an hour. The relative photoluminescence quantum yield observed for Br-rich regions (em. max 530 nm) is nearly 2 orders of magnitude lower than that of I-rich regions (em. max 760 nm) and arises from the fact that I-rich regions serve as sinks for photogenerated charge carriers. Understanding such cascading charge transfer to localized sites could further enable the design of gradient halide structures in mixed halide systems.
Minimizing photoinduced segregation in mixed halide lead perovskites is important for achieving stable photovoltaic performance. The shift in the absorption and the rate of formation of iodide-and bromide-rich regions following visible excitation of mixed halide lead perovskites is found to strongly depend on the halide ion concentration. Slower formation and recovery rates observed in halide-deficient films indicate the involvement of defect sites in influencing halide phase segregation. At higher halide concentrations (in stoichiometric excess), segregation effects become less prominent, as evidenced by faster recovery kinetics. These results suggest that light-induced compositional segregation can be minimized in mixed halide perovskite films by using excess halide ions. The findings from this study further reflect the importance of halide ion post-treatment of perovskite films to improve their solar cell performance.
Varying the halide ratio (e.g., Br(-):I(-)) is a convenient approach to tune the bandgap of organic lead halide perovskites. The complexation between Pb(2+) and halide ions is the primary step in dictating the overall composition, and optical properties of the annealed perovskite structure. The complexation between Pb(2+) and Br(-) is nearly 7 times greater than the complexation between Pb(2+) and I(-), thus making Br(-) a dominant binding species in mixed halide systems. Emission and transient absorption measurements show a strong dependence of excited state behavior on the composition of halide ions employed in the precursor solution. When excess halide (X = Br(-) and I(-)) are present in the precursor solution (0.3 M PbX2 and 0.9 M CH3NH3X), the exclusive binding of Pb(2+) with Br(-) results in the formation of CH3NH3PbBr3 perovskites as opposed to mixed halide perovskite.
The optical and electronic properties of quantum dots (QDs), which are drastically affected by their size, have a major impact on their performance in devices such as solar cells. We now report the size-dependent solar cell performance for CuInS 2 QDs capped with 1dodecanethiol. Pyramidal shaped CuInS 2 QDs with diameters between 2.9 and 5.3 nm have been synthesized and assembled on mesoscopic TiO 2 films by electrophoretic deposition. Time-resolved emission and transient absorption spectroscopy measurements have ascertained the role of internal and surface defects in determining the solar cell performance. An increase in power conversion efficiency (PCE) was observed with the increasing size of QDs, with maximum values of 2.14 and 2.51% for 3.9 and 4.3 nm size particles, respectively. The drop in PCE observed for larger QDs (5.3 nm) is attributed to decreased charge separation following bandgap excitation. Because the origin of photocurrent generation in CuInS 2 QDSC arises from the defect-dominated charge carriers, it offers the opportunity to further improve the efficiency by controlling these defect concentrations.
Mixed halide perovskites
are one of the promising candidates in
developing solar cells and light-emitting diodes (LEDs), among other
applications, because of their tunable optical properties. Nonetheless,
photoinduced phase segregation, by formation of segregated Br-rich
and I-rich domains, limits the overall applicability. We tracked the
phase segregation with increasing crystalline size of CsPbBr3–xIx and their photoluminescence
under continuous-wave laser irradiation (405 nm, 10 mW cm–2) and observed the occurrence of the phase segregation from the threshold
size of 46 ± 7 nm. These results have an outstanding agreement
with the diffusion length (45.8 nm) calculated also experimentally
from the emission lifetime and segregation rates. Furthermore, through
Kelvin probe force microscopy, we confirmed the correlation between
the phase segregation and the reversible halide ion migration among
grain centers and boundaries. These results open a way to achieve
segregation-free mixed halide perovskites and improve their performances
in optoelectronic devices.
Inspired by the outstanding optoelectronic properties reported for all-inorganic halide perovskite quantum dots (QDs), we have evaluated the potential of these materials toward the photocatalytic and photoelectrochemical degradation of organic compounds, taking the oxidation of 2-mercaptobenzothiazole (MBT) as a proof-of-concept. First, we determined electrochemically the energy levels of dispersions of perovskite QDs with different band gaps induced by the different ratios between halides (Br and I) and metallic cations (Pb and Sn). Then, we selected CsPbBr 3 QDs to demonstrate the photocatalytic and photoelectrochemical oxidation of MBT, confirming that hole injection takes place from CsPbBr 3 QDs to MBT, resulting in the total degradation of MBT as evidenced by electrospray mass spectrometry analyses. Although the stability and toxicity of these QDs are major issues to address in the near future, the results obtained in the present study open promising perspectives for the implementation of solar-driven catalytic strategies based on these fascinating materials.
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