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

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)

Energy transfer from perovskite nanocrystals to dye molecules does not occur by FRET

Single formamidinium lead bromide (FAPbBr(3)) perovskite nanocubes, approximately 10 nm in size, have extinction cross sections orders of magnitude larger than single dye molecules and can therefore be used to photoexcite one single dye molecule within their immediate vicinity by means of excitation-energy transfer (EET). The rate of photon emission by the single dye molecule is increased by 2 orders of magnitude under excitation by EET compared to direct excitation at the same laser fluence. Because the dye cannot accommodate biexcitons, NC biexcitons are filtered out by EET, giving rise to up to an order-of-magnitude improvement in the fidelity of photon antibunching. We demonstrate here that, contrary to expectation, energy transfer from the nanocrystal to dye molecules does not depend on the spectral line widths of the donor and acceptor and is therefore not governed by Forster's theory of resonance energy transfer (FRET). Two different cyanine dye acceptors with substantially different spectral overlaps with the nanocrystal donor show a similar light-harvesting capability. Cooling the sample from room temperature to 5 K reduces the average transition line widths 25-fold but has no apparent effect on the number of molecules emitting, i.e., on the spatial density of single dye molecules being photoexcited by single nanocrystals. Narrow zero-phonon lines are identified for both donor and acceptor, with an energetic separation of over 40 times the line width, implying a complete absence of spectral overlap-even though EET is evident. Both donor and acceptor exhibit spectral fluctuations, but no correlation is apparent between the jitter, which controls spectral overlap, and the overall light harvesting. We conclude that the energy transfer process is fundamentally nonresonant, implying effective energy dissipation in the perovskite donor because of strong electron-phonon coupling of the carriers comprising the exciton. The work highlights the importance of performing cryogenic spectroscopy to reveal the underlying mechanisms of energy transfer in complex donor-acceptor systems

Nanoscale-Resolved Surface-to-Bulk Electron Transport in CsPbBr3Perovskite

Describing the nanoscale charge carrier transport at surfaces and interfaces is fundamental for designing high-performance optoelectronic devices. To achieve this, we employ time- and angle-resolved photoelectron spectroscopy with ultraviolet pump and extreme ultraviolet probe pulses. The resulting high surface sensitivity reveals an ultrafast carrier population decay associated with surface-to-bulk transport, which was tracked with a sub-nanometer spatial resolution normal to the surface, and on a femtosecond time scale, in the case of the inorganic CsPbBr3 lead halide perovskite. The decay time exhibits a pronounced carrier density dependence, which is attributed via modeling to enhanced diffusive transport and concurrent recombination. The transport is found to approach an ordinary diffusive regime, limited by electron-hole scattering, at the highest excitation fluences. This approach constitutes an important milestone in our capability to probe hot-carrier transport at solid interfaces with sub-nanometer resolution in a theoretically and experimentally challenging, yet technologically relevant, high-carrier-density regime

Self‐Assembly of Proteinaceous Shells around Positively Charged Gold Nanomaterials Enhances Colloidal Stability in High‐Ionic‐Strength Buffers

ISSN:1439-4227ISSN:1439-763