High-resolution remote thermography using luminescent low-dimensional tin-halide perovskites

While metal-halide perovskites have recently revolutionized research in optoelectronics through a unique combination of performance and synthetic simplicity, their low-dimensional counterparts can further expand the field with hitherto unknown and practically useful optical functionalities. In this context, we present the strong temperature dependence of the photoluminescence (PL) lifetime of low-dimensional, perovskite-like tin-halides, and apply this property to thermal imaging with a high precision of 0.05 {\deg}C. The PL lifetimes are governed by the heat-assisted de-trapping of self-trapped excitons, and their values can be varied over several orders of magnitude by adjusting the temperature (up to 20 ns {\deg}C-1). Typically, this sensitive range spans up to one hundred centigrade, and it is both compound-specific and shown to be compositionally and structurally tunable from -100 to 110 {\deg} C going from [C(NH2)3]2SnBr4 to Cs4SnBr6 and (C4N2H14I)4SnI6. Finally, through the innovative implementation of cost-effective hardware for fluorescence lifetime imaging (FLI), based on time-of-flight (ToF) technology, these novel thermoluminophores have been used to record thermographic videos with high spatial and thermal resolution.Comment: 25 pages, 4 figure

Coherent spin dynamics of electrons and holes in CsPbBr3_3 perovskite crystals

The lead halide perovskites demonstrate huge potential for optoelectronic applications, high energy radiation detectors, light emitting devices and solar energy harvesting. Those materials exhibit strong spin-orbit coupling enabling efficient optical orientation of carrier spins in perovskite-based devices with performance controlled by a magnetic field. Perovskites are promising for spintronics due to substantial bulk and structure inversion asymmetry, however, their spin properties are not studied in detail. Here we show that elaborated time-resolved spectroscopy involving strong magnetic fields can be successfully used for perovskites. We perform a comprehensive study of high-quality CsPbBr$_3$ crystals by measuring the exciton and charge carrier $g$-factors, spin relaxation times and hyperfine interaction of carrier and nuclear spins by means of coherent spin dynamics. Owing to their "inverted" band structure, perovskites represent appealing model systems for semiconductor spintronics exploiting the valence band hole spins, while in conventional semiconductors the conduction band electrons are considered for spin functionality.Comment: 8 pages, 3 figures + supplementary informatio

Scalable fabrication of efficient p-n junction lead sulfide quantum dot solar cells

Nowadays, the best lead sulfide (PbS) colloidal quantum dot (CQD) solar cells are primarily demonstrated in the n-p structure, while the p-n structure is significantly less developed. This technological gap between the n-p and p-n structures is much more distinct than in cases of other solution-processable photovoltaic technologies like perovskites and polymers. Here, we propose a scalable fabrication strategy for efficient PbS QD solar cells with p-n structure. An industrially suited blade-coating technique has been used to deposit both n-type and p-type QD layers. The obtained solar cells demonstrated power conversion efficiency of 9%, thus, commensurate to the record device efficiency with this architecture fabricated with a non-scalable technique. The availability of both p-n and n-p structures fabricated from scalable methods may promote the future integration of the PbS QDs into tandem devices together with other solution-processable materials to exploit the most prominent benefits of the PbS QDs, such as infrared absorption.</p

Stoichiometric control of the density of states in PbS colloidal quantum dot solids

Colloidal quantum dots, and nanostructured semiconductors in general, carry the promise of overcoming the limitations of classical materials in chemical and physical properties and in processability. However, sufficient control of electronic properties, such as carrier concentration and carrier mobility, has not been achieved until now, limiting their application. In bulk semiconductors, modifications of electronic properties are obtained by alloying or doping, an approach that is not viable for structures in which the surface is dominant. The electronic properties of PbS colloidal quantum dot films are fine-tuned by adjusting their stoichiometry, using the large surface area of the nanoscale building blocks. We achieve an improvement ofmore than two orders ofmagnitude in the holemobility, from below 10(-3) to above 0.1 cm(2)/N.s, by substituting the iodide ligands with sulfide while keeping the electron mobility stable (similar to 1 cm(2)/V.s). This approach is not possible in bulk semiconductors, and the developed method will likely contribute to the improvement of solar cell efficiencies through better carrier extraction and to the realization of complex (opto) electronic devices

The squeezed dark nuclear spin state in lead halide perovskites

Coherent many-body states are highly promising for robust quantum information processing. While far-reaching theoretical predictions have been made for various implementations, direct experimental evidence of their appealing properties can be challenging. Here, we demonstrate optical manipulation of the nuclear spin ensemble in the lead halide perovskite semiconductor FAPbBr3 (FA = formamidinium), targeting a long-postulated collective dark state that is insensitive to optical pumping after its build-up. Via optical orientation of localized hole spins we drive the nuclear many-body system into this entangled state, requiring a weak magnetic field of only a few milli-Tesla strength at cryogenic temperatures. During its fast establishment, the nuclear polarization along the optical axis remains small, while the transverse nuclear spin fluctuations are strongly reduced, corresponding to spin squeezing as evidenced by a strong violation of the generalized nuclear squeezing-inequality with ξs < 0.5. The dark state corresponds to an ~35-body entanglement between the nuclei. Dark nuclear spin states can be exploited to store quantum information benefiting from their long-lived many-body coherence and to perform quantum measurements with a precision beyond the standard limit

Scalable PbS Quantum Dot Solar Cell Production by Blade Coating from Stable Inks

The recent development of phase transfer ligand exchange methods for PbS quantum dots (QD) has enhanced the performance of quantum dots solar cells and greatly simplified the complexity of film deposition. However, the dispersions of PbS QDs (inks) used for film fabrication often suffer from colloidal instability, which hinders large-scale solar cell production. In addition, the wasteful spin-coating method is still the main technique for the deposition of QD layer in solar cells. Here, we report a strategy for scalable solar cell fabrication from highly stable PbS QD inks. By dispersing PbS QDs capped with CH3NH3PbI3 in 2,6-difluoropyridine (DFP), we obtained inks that are colloidally stable for more than 3 months. Furthermore, we demonstrated that DFP yields stable dispersions even of large diameter PbS QDs, which are of great practical relevance owing to the extended coverage of the near-infrared region. The optimization of blade-coating deposition of DFP-based inks enabled the fabrication of PbS QD solar cells with power conversion efficiencies of up to 8.7%. It is important to underline that this performance is commensurate with the devices made by spin coating of inks with the same ligands. A good shelf life-time of these inks manifests itself in the comparatively high photovoltaic efficiency of 5.8% obtained with inks stored for more than 120 days

Enhancing Quantum Dot Solar Cells Stability with a Semiconducting Single-Walled Carbon Nanotubes Interlayer Below the Top Anode

Semiconducting single-walled carbon nanotubes (s-SWNTs) are used as a protective interlayer between the lead sulfide colloidal quantum dot (PbS CQD) active layer and the anode of the solar cells (SCs). The introduction of the carbon nanotubes leads to increased device stability, with 85% of the initial performance retained after 100 h exposure to simulated solar light in ambient condition. This is in sharp contrast with the behavior of the device without s-SWNTs, for which the photoconversion efficiency, the open circuit voltage, the short-circuit current, and the fill factor all experiencing a sharp decrease. Therefore, the inclusion of s-SWNT as interlayer in CQD SCs, give rise to SCs of identical efficiency (above 8.5%) and prevents their performance degradation

Exploiting the Lability of Metal Halide Perovskites for Doping Semiconductor Nanocomposites

Cesium lead halides have intrinsically unstable crystal lattices and easily transform within perovskite and nonperovskite structures. In this work, we explore the conversion of the perovskite CsPbBr3 into Cs4PbBr6 in the presence of PbS at 450 °C to produce doped nanocrystal-based composites with embedded Cs4PbBr6 nanoprecipitates. We show that PbBr2 is extracted from CsPbBr3 and diffuses into the PbS lattice with a consequent increase in the concentration of free charge carriers. This new doping strategy enables the adjustment of the density of charge carriers between 1019 and 1020 cm-3, and it may serve as a general strategy for doping other nanocrystal-based semiconductors.M.C. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 665385. ICN2 acknowledges funding from Generalitat de Catalunya 2017 SGR 327. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706) and is funded by the CERCA Programme/Generalitat de Catalunya. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 823717 – ESTEEM3. M.V.K. acknowledges the support by the European Research Council under the Horizon 2020 Framework Program (ERC Consolidator Grant SCALE-HALO Grant Agreement No. 819740) and by FET-OPEN project no. 862656 (DROP-IT)

Lead-dominated hyperfine interaction impacting the carrier spin dynamics in halide perovskites

The outstanding optical quality of lead halide perovskites inspires studies of their potential for the optical control of carrier spins as pursued in other materials. Entering largely uncharted territory, time-resolved pump–probe Kerr rotation is used to explore the coherent spin dynamics of electrons and holes in bulk formamidinium caesium lead iodine bromide (FA0.9Cs0.1PbI2.8Br0.2) and to determine key parameters characterizing interactions of their spins, such as the g-factors and relaxation times. The demonstrated long spin dynamics and narrow g-factor distribution prove the perovskites as promising competitors for conventional semiconductors in spintronics. The dynamic nuclear polarization via spin-oriented holes is realized and the identification of the lead (207Pb) isotope in optically detected nuclear magnetic resonance proves that the hole–nuclei interaction is dominated by the lead ions. A detailed theoretical analysis accounting for the specifics of the lead halide perovskite materials allows the evaluation of the underlying hyperfine interaction constants, both for electrons and holes. Recombination and spin dynamics evidence that at low temperatures, photogenerated electrons and holes are localized at different regions of the perovskite crystal, resulting in their long lifetimes up to 44 μs. The findings form the base for the tailored development of spin-optoelectronic applications for the large family of lead halide perovskites and their nanostructures

The Landé factors of electrons and holes in lead halide perovskites: universal dependence on the band gap

The Landé or g-factors of charge carriers are decisive for the spin-dependent phenomena in solids and provide also information about the underlying electronic band structure. We present a comprehensive set of experimental data for values and anisotropies of the electron and hole Landé factors in hybrid organic-inorganic (MAPbI3, MAPb(Br0.5Cl0.5)3, MAPb(Br0.05Cl0.95)3, FAPbBr3, FA0.9Cs0.1PbI2.8Br0.2, MA=methylammonium and FA=formamidinium) and all-inorganic (CsPbBr3) lead halide perovskites, determined by pump-probe Kerr rotation and spin-flip Raman scattering in magnetic fields up to 10 T at cryogenic temperatures. Further, we use first-principles density functional theory (DFT) calculations in combination with tight-binding and k ⋅ p approaches to calculate microscopically the Landé factors. The results demonstrate their universal dependence on the band gap energy across the different perovskite material classes, which can be summarized in a universal semi-phenomenological expression, in good agreement with experiment