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Register a new userStructural phase transitions and photoluminescence mechanism in a layer of 3D hybrid perovskite nanocrystals
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Although the structural phase transitions in single-crystal hybrid methyl-ammonium (MA) lead halide perovskites (MAPbX3, X = Cl, Br, I) are common phenomena, they have never been observed in the corresponding nanocrystals. Here we demonstrate that two-photon-excited photoluminescence (PL) spectroscopy is capable of monitoring the structural phase transitions in MAPbX3 nanocrystals because nonlinear susceptibilities govern the light absorption rates. We provide experimental evidence that the orthorhombic-to-tetragonal structural phase transition in a single layer of 20-nm-sized 3D MAPbBr3 nanocrystals is spread out within the 70 - 140 K range. This structural phase instability range arises because, unlike in single-crystal MAPbX3, free rotations of MA ions in the corresponding nanocrystals are no longer restricted by a long-range MA dipole order. The resulting configurational entropy loss can be even enhanced by the interfacial electric field arising due to charge separation at the MAPbBr3/ZnO heterointerface, extending the orthorhombic-to-tetragonal structural phase instability range from 70 to 230 K. We conclude that the weak sensitivity of conventional one-photon-excited PL spectroscopy to the structural phase transitions in 3D MAPbX3 nanocrystals results from the structural phase instability providing negligible distortions of PbX6 octahedra. In contrast, the intensity of two-photon-excited PL and electric-field-induced one-photon-excited PL still remains sensitive enough to weak structural distortions due to the higher rank tensor nature of nonlinear susceptibilities involved. We also show that room-temperature PL originates from the radiative recombination of the optical-phonon vibrationally excited polaronic quasiparticles with energies might exceed the ground-state Frohlich polaron and Rashba energies due to optical-phonon bottleneck.
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The dynamical and static Rashba effects in hybrid methylammonium (MA) lead halide perovskites have recently been theoretically predicted. However, only the static effect was experimentally confirmed so far. Here we report on the dynamical Rashba effect observed using snapshot transient absorption spectral imaging with 400 nm pumping for a fully encapsulated film of 20-nm-sized 3D MAPbBr3 nanocrystals. The effect causes a 240 meV splitting of the lowest-energy absorption bleaching band, initially appearing over sub-ps timescale and progressively stabilizing to 60 meV during 500 ps. The integrated intensities of the split subbands demonstrate a photon-helicity-dependent asymmetry, thus proving the Rashba-type splitting and providing direct experimental evidence for the Rashba spin-split edge states in lead halide perovskite materials. The ultrafast dynamics is governed by the relaxation of two-photon-excited electrons in the Rashba spin-split system caused by a built-in electric field originating from dynamical charge separation in the entire MAPbBr3 nanocrystal.
We study the origin of the cubic to tetragonal and tetragonal to monoclinic structural transitions in KCrF3, and the associated change in orbital order, paying particular attention to the relevance of super-exchange in both phases. We show that super-exchange is not the main mechanism driving these transitions. Specifically, it is not strong enough to be responsible for the high-temperature cubic to tetragonal transition and does not yield the type of orbital order observed in the monoclinic phase. The energy difference between the tetragonal and the monoclinic structure is tiny, and most likely results from the interplay between volume, covalency, and localization effects. The transition is rather driven by Slater exchange than super-exchange. Nevertheless, once the monoclinic distortions are present, super-exchange helps in stabilizing the low symmetry structure. The orbital order we obtain for this monoclinic phase is consistent with the magnetic transition at 80 K.
Integrated optical devices able to control light matter interactions on the nanoscale have attracted the attention of the scientific community in recent years. However, most of these devices are based on silicon waveguides, limiting their use for telecommunication wavelengths. In this contribution, we propose an integrated device that operates with light in the visible spectrum. The proposed device is a hybrid structure consisting of a high-refractive-index layer placed on top of an ion-exchanged glass waveguide. We demonstrate that this hybrid structure serves as an efficient light coupler for the excitation of nanoemitters. The numerical and experimental results show that the device can enhance the electromagnetic field confinement up to 11 times, allowing a higher photoluminescence signal from nanocrystals placed on its surface. The designed device opens new perspectives in the generation of new optical devices suitable for quantum information or for optical sensing.
Excitonic/electronic coupling and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a collective low energy emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assembled superlattices. This is demonstrated by using CsPbBr3 nanocrystal superlattices under room temperature and cryogenic micro-photoluminescence spectroscopy. It is shown that keeping such structures under vacuum, a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days. As a result, a narrow, low energy emission peak is observed at 4 K with a concomitant shortening of the photoluminescence lifetime due to the energy transfer between nanocrystals. When exposed to air, self-assembled CsPbBr3 nanocrystals develop bulk-like CsPbBr3 particles on top of the superlattices. At 4 K, these particles produce a distribution of narrow, low energy emission peaks with short lifetimes and excitation fluence-dependent, oscillatory decays, resembling the features of superfluorescence. Overall, the reactivity of CsPbBr3 nanocrystals dramatically alters the emission of their assemblies, which should not be overlooked when studying collective optoelectronic properties nor confused with superfluorescence effects.
Three different film systems have been systematically investigated to understand the effects of strain and substrate constraint on the phase transitions of perovskite films. In SrTiO$_3$ films, the phase transition temperature T$_C$ was determined by monitoring the superlattice peaks associated with rotations of TiO$_6$ octahedra. It is found that T$_C$ depends on both SrTiO$_3$ film thickness and SrRuO$_3$ buffer layer thickness. However, lattice parameter measurements showed no sign of the phase transitions, indicating that the tetragonality of the SrTiO$_3$ unit cells was no longer a good order parameter. This signals a change in the nature of this phase transition, the internal degree of freedom is decoupled from the external degree of freedom. The phase transitions occur even without lattice relaxation through domain formation. In NdNiO$_3$ thin films, it is found that the in-plane lattice parameters were clamped by the substrate, while out-of-plane lattice constant varied to accommodate the volume change across the phase transition. This shows that substrate constraint is an important parameter for epitaxial film systems, and is responsible for the suppression of external structural change in SrTiO$_3$ and NdNiO$_3$ films. However, in SrRuO$_3$ films we observed domain formation at elevated temperature through x-ray reciprocal space mapping. This indicated that internal strain energy within films also played an important role, and may dominate in some film systems. The final strain states within epitaxial films were the result of competition between multiple mechanisms and may not be described by a single parameter.
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