Experimental evidence for defect tolerance in Pb-halide perovskites.

The term defect tolerance (DT) is used often to rationalize the exceptional optoelectronic properties of halide perovskites (HaPs) and their devices. Even though DT lacked direct experimental evidence, it became a "fact" in the field. DT in semiconductors implies that structural defects do not translate to electrical and optical effects (e.g., due to charge trapping), associated with such defects. We present pioneering direct experimental evidence for DT in Pb-HaPs by comparing the structural quality of 2-dimensional (2D), 2D-3D, and 3D Pb-iodide HaP crystals with their optoelectronic characteristics using high-sensitivity methods. Importantly, we get information from the materials' bulk because we sample at least a few hundred nanometers, up to several micrometers, from the sample's surface, which allows for assessing intrinsic bulk (and not only surface-) properties of HaPs. The results point to DT in 3D, 2D-3D, and 2D Pb-HaPs. Overall, our data provide an experimental basis to rationalize DT in Pb-HaPs. These experiments and findings will help the search for and design of materials with real DT.

Free Carrier Emergence and Onset of Electron-Phonon Coupling in Methylammonium Lead Halide Perovskite Films.

Sub-10 fs resolution pump-probe experiments on methylammonium lead halide perovskite films are described. Initial response to photoexcitation is assigned to localized hot excitons which dissociate to free carriers. This is attested to by band integrals of the pump-probe spectra where photoinduced bleaching rises abruptly 20 fs after photoexcitation. Later stages of spectral evolution are consistent with hot carrier cooling, during which state filling induced bleaching of interband and exciton transitions curiously more than doubles. Electron coupling to optical phonons is observed as periodic spectral modulations in the pump-probe data of both films. Fourier analysis identifies active phonons at ∼100 and 300 wavenumbers pertaining to the lead-halide framework and organic cation motions, respectively. Coupling strengths estimated from the depth of these modulations are in the weak coupling limit, in agreement with values extracted from temperature dependent emission line shape analysis. These findings support free carriers in these materials existing as large polarons. Accordingly, these modes are probably not dictating the moderate carrier mobility in this material.

Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors.

Depletion region effect of highly efficient hole conductor free CH3NH3PbI3 perovskite solar cells.

The inorganic-organic perovskite is currently attracting a lot of attention due to its use as a light harvester in solar cells. The large absorption coefficients, high carrier mobility and good stability of organo-lead halide perovskites present good potential for their use as light harvesters in mesoscopic heterojunction solar cells. This work concentrated on a unique property of the lead halide perovskite, its function simultaneously as a light harvester and a hole conductor in the solar cell. A two-step deposition technique was used to optimize the perovskite deposition and to enhance the solar cell efficiency. It was revealed that the photovoltaic performance of the hole conductor free perovskite solar cell is strongly dependent on the depletion layer width which was created at the TiO2-CH3NH3PbI3 junction. X-ray diffraction measurements indicate that there were no changes in the crystallographic structure of the CH3NH3PbI3 perovskite over time, which supports the high stability of these hole conductor free perovskite solar cells. Furthermore, the power conversion efficiency of the best cells reached 10.85% with a fill factor of 68%, a Voc of 0.84 V, and a Jsc of 19 mA cm(-2), the highest efficiency to date of a hole conductor free perovskite solar cell.

Static and Dynamic Disorder in Formamidinium Lead Bromide Single Crystals.

We show that formamidinium-based crystals are distinct from methylammonium-based halide perovskite crystals because their inorganic sublattice exhibits intrinsic local static disorder that coexists with a well-defined average crystal structure. Our study combines terahertz-range Raman scattering with single-crystal X-ray diffraction and first-principles calculations to probe the evolution of inorganic sublattice dynamics with temperature in the range of 10-300 K. The temperature evolution of the Raman spectra shows that low-temperature, local static disorder strongly affects the crystal structural dynamics and phase transitions at higher temperatures.

Phonon-driven intra-exciton Rabi oscillations in CsPbBr3 halide perovskites.

Coupling electromagnetic radiation with matter, e.g., by resonant light fields in external optical cavities, is highly promising for tailoring the optoelectronic properties of functional materials on the nanoscale. Here, we demonstrate that even internal fields induced by coherent lattice motions can be used to control the transient excitonic optical response in CsPbBr3 halide perovskite crystals. Upon resonant photoexcitation, two-dimensional electronic spectroscopy reveals an excitonic peak structure oscillating persistently with a 100-fs period for up to ~2 ps which does not match the frequency of any phonon modes of the crystals. Only at later times, beyond 2 ps, two low-frequency phonons of the lead-bromide lattice dominate the dynamics. We rationalize these findings by an unusual exciton-phonon coupling inducing off-resonant 100-fs Rabi oscillations between 1s and 2p excitons driven by the low-frequency phonons. As such, prevailing models for the electron-phonon coupling in halide perovskites are insufficient to explain these results. We propose the coupling of characteristic low-frequency phonon fields to intra-excitonic transitions in halide perovskites as the key to control the anharmonic response of these materials in order to establish new routes for enhancing their optoelectronic properties.

Strongly Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites.

Recent investigations of two-dimensional (2D) hybrid organic-inorganic halide perovskites (HHPs) indicate that their optical and electronic properties are dominated by strong coupling to thermal fluctuations. While the optical properties of 2D-HHPs have been extensively studied, a comprehensive understanding of electron-phonon interactions is limited because little is known about their structural dynamics. This is partially because the unit cells of 2D-HHPs contain many atoms. Therefore, the thermal fluctuations are complex and difficult to elucidate in detail. To overcome this challenge, we use polarization-orientation Raman spectroscopy and ab initio calculations to compare the structural dynamics of the prototypical 2D-HHPs [(BA)2PbI4 and (PhE)2PbI4] to their three-dimensional (3D) counterpart, MAPbI3. Comparison to the simpler, 3D MAPbI3 crystal shows clear similarities with the structural dynamics of (BA)2PbI4 and (PhE)2PbI4 across a wide temperature range. The analogy between the 3D and 2D crystals allows us to isolate the effect of the organic cation on the structural dynamics of the inorganic scaffold of the 2D-HHPs. Furthermore, using this approach, we uncover the mechanism of the order-disorder phase transition of (BA)2PbI4 (274 K) and show that it involves relaxation of octahedral tilting coupled to anharmonic thermal fluctuations. These anharmonic fluctuations are important because they induce charge carrier localization and affect the optoelectronic performance of these materials.

Electrical Characterization of Individual Cesium Lead Halide Perovskite Nanowires Using Conductive AFM.

Perovskite nanostructures have attracted much attention in recent years due to their suitability for a variety of applications such as photovoltaics, light-emitting diodes (LEDs), nanometer-size lasing, and more. These uses rely on the conductive properties of these nanostructures. However, electrical characterization of individual, thin perovskite nanowires has not yet been reported. Here, conductive atomic force microscopy characterization of individual cesium lead halide nanowires is presented. Clear differences are observed in the conductivity of nanowires containing only bromide and nanowires containing a mixture of bromide and iodide. The differences are attributed to a higher density of crystalline defects, deeper trap states, and higher inherent conductivity for nanowires with mixed bromide-iodide content.

Cell refinement of CsPbBr3 perovskite nanoparticles and thin films.

In this work, we performed a detailed study of the phase transformations and structural unit cell parameters of CsPbBr3 nanoparticles (NPs) and thin films. In situ X-ray diffraction patterns were acquired as a function of temperature, where the positions and widths of the diffraction peaks were systematically tracked upon heating and cooling down to room temperature (RT). Scanning electron microscopy provides physical insight on the CsPbBr3 thin films upon annealing and transmission electron microscopy gives physical and crystallographic information for the CsPbBr3 NPs using electron diffraction. The secondary phase(s) CsPb2Br5 (and CsPb4Br6) are clearly observed in the XRD patterns of both nanoparticles and thin films upon heating to 500 K, whilst from 500 K to 595 K, these phases remain in small amounts and are kept like this upon cooling down to RT. However, in the case of thin films, the CsPb2Br5 secondary phase disappears completely above 580 K and pure cubic CsPbBr3 is observed up to 623 K. The CsPbBr3 phase is then kept upon cooling down to RT, achieving pure CsPbBr3 phase. This study provides detailed understanding of the phase behavior vs. temperature of CsPbBr3 NPs and thin films, which opens the way to pure CsPbBr3 phase, an interesting material for optoelectronic applications.

Reflectivity Effects on Pump-Probe Spectra of Lead Halide Perovskites: Comparing Thin Films versus Nanocrystals.

Due to the sizable refractive index of lead halide perovskites, reflectivity off their interface with air exceeds 15%. This has prompted a number of investigations into the prominence of photoreflective contributions to pump-probe data in these materials, with conflicting results. Here we report experiments aimed at assessing this by comparing transient transmission from lead halide perovskite films and weakly quantum confined nanocrystals of cesium lead iodide (CsPbI3) perovskite. By analyzing how complex refractive index changes impact the two experiments, results demonstrate that changes in absorption and not reflection dominate transient transmission measurements in thin films of these materials. None of the characteristic spectral signatures reported in such experiments are exclusively due to or even strongly affected by changes in sample reflectivity. This finding is upheld by another experiment where a methyl ammonium lead iodide (MAPbI3) perovskite film was formed on high-index flint glass and probed after pump irradiation from either face of the sample. We conclude that interpretations of ultrafast pump-probe experiments on thin perovskite films in terms of photoinduced changes in absorption alone are qualitatively sound, requiring relatively minor adjustments to factor in photoreflective effects.

Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution.

In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking their growth by high-resolution transmission electron microscopy and size distribution analysis. As a result, we are able to provide a detailed model for the kinetics of their growth. It was observed that the CsPbI3 NPs exhibit focusing of the size distribution in the first 20 seconds of growth, followed by de-focusing over longer growth durations, while the CsPbBr3 NPs show de-focusing of the size distribution starting from the beginning of the growth. The monomer concentration is depleted faster in the case of CsPbBr3 than in the case of CsPbI3, due to faster diffusion of the monomers, which increases the critical radius and results in de-focusing of the population. Accordingly, focusing is not observed within 40 seconds of growth in the case of CsPbBr3. This study provides important knowledge on how to achieve a narrow size distribution of cesium lead halide perovskite NPs when generating large amounts of these promising, highly luminescent NPs.

Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials.

The photochemical stability of encapsulated films of mixed halide perovskites with a range of MAPb(I1-x Brx )3 (MA=methylammonium) compositions (solid solutions) was investigated under accelerated stressing using concentrated sunlight. The relevance of accelerated testing to standard operational conditions of solar cells was confirmed by comparison to degradation experiments under outdoor sunlight exposure. We found that MAPbBr3 films exhibited no degradation, while MAPbI3 and mixed halide MAPb(I1-x Brx )3 films decomposed yielding crystallization of inorganic PbI2 accompanied by degradation of the perovskite solar light absorption, with faster absorption degradation in mixed halide films. The crystal coherence length was found to correlate with the stability of the films. We postulate that the introduction of Br into the mixed halide solid solution stressed its structure and induced more structural defects and/or grain boundaries compared to pure halide perovskites, which might be responsible for the accelerated degradation. Hence, the cause for accelerated degradation may be the increased defect density rather than the chemical composition of the perovskite materials.

Temperature- and Component-Dependent Degradation of Perovskite Photovoltaic Materials under Concentrated Sunlight.

We report on accelerated degradation testing of MAPbX3 films (X = I or Br) by exposure to concentrated sunlight of 100 suns and show that the evolution of light absorption and the corresponding structural modifications are dependent on the type of halide ion and the exposure temperature. One hour of such exposure provides a photon dose equivalent to that of one sun exposure for 100 hours. The degradation in absorption of MAPbI3 films after exposure to 100 suns for 60 min at elevated sample temperature (∼45-55 °C), due to decomposition of the hybrid perovskite material, is documented. No degradation was observed after exposure to the same sunlight concentration but at a lower sample temperature (∼25 °C). No photobleaching or decomposition of MAPbBr3 films was observed after exposure to similar stress conditions (light intensity, dose, and temperatures). Our results indicate that the degradation is highly dependent on the hybrid perovskite composition and can be light- and thermally enhanced.