Tuning Structure and Excitonic Properties of 2D Ruddlesden-Popper Germanium, Tin, and Lead Iodide Perovskites via Interplay between Cations.

The compositional tunability of 2D metal halide perovskites enables exploration of diverse semiconducting materials with different structural features. However, rationally tuning the 2D perovskite structures to target physical properties for specific applications remains challenging, especially for lead-free perovskites. Here, we study the effect of the interplay of the B-site (Ge, Sn, and Pb), A-site (cesium, methylammonium, and formamidinium), and spacer cations on the structure and optical properties of a new series of 2D Ruddlesden-Popper perovskites using the previously unreported spacer cation 4-bromo-2-fluorobenzylammonium (4Br2FBZ). We report eight new crystal structures and study the consequence of varying the B-site (Pb, Sn, Ge) and dimension (n = 1, 2, vs 3D). Dimension strongly influences local distortion and structural symmetry, and the increased octahedral tilting and lone pair effects in Ge perovskites lead to a polar n = 2 perovskite that exhibits second harmonic generation, (4Br2FBZ)2(Cs)Ge2I7. In contrast, the analogous Sn and Pb perovskites remain centrosymmetric, but the B-site metal influences the photoluminescence properties. The Pb perovskites exhibit broad, defect-mediated emission at low temperature, whereas the Sn perovskites show purely excitonic emission over the entire temperature range, but the carrier recombination dynamics depend on dimensionality and dark excitonic states. Wholistic understanding of these differences that arise based on cations and dimensionality can guide the rational materials design of 2D perovskites for targeting physical properties for optoelectronic applications based on the interplay of cations and the connectivity of the inorganic framework.

Metamaterial Enhancement of Metal-Halide Perovskite Luminescence.

Metal-halide perovskites are rapidly emerging as solution-processable optical materials for light-emitting applications. Here, we adopt a plasmonic metamaterial approach to enhance photoluminescence emission and extraction of methylammonium lead iodide (MAPbI3) thin films based on the Purcell effect. We show that hybridization of the active metal-halide film with resonant nanoscale sized slits carved into a gold film can yield more than 1 order of magnitude enhancement of luminescence intensity and nearly 3-fold reduction of luminescence lifetime corresponding to a Purcell enhancement factor of more than 300. These results show the effectiveness of resonant nanostructures in controlling metal-halide perovskite light emission properties over a tunable spectral range, a viable approach toward highly efficient perovskite light-emitting devices and single-photon emitters.

Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites.

Hybrid organic-inorganic semiconductors feature complex lattice dynamics due to the ionic character of the crystal and the softness arising from non-covalent bonds between molecular moieties and the inorganic network. Here we establish that such dynamic structural complexity in a prototypical two-dimensional lead iodide perovskite gives rise to the coexistence of diverse excitonic resonances, each with a distinct degree of polaronic character. By means of high-resolution resonant impulsive stimulated Raman spectroscopy, we identify vibrational wavepacket dynamics that evolve along different configurational coordinates for distinct excitons and photocarriers. Employing density functional theory calculations, we assign the observed coherent vibrational modes to various low-frequency (≲50 cm-1) optical phonons involving motion in the lead iodide layers. We thus conclude that different excitons induce specific lattice reorganizations, which are signatures of polaronic binding. This insight into the energetic/configurational landscape involving globally neutral primary photoexcitations may be relevant to a broader class of emerging hybrid semiconductor materials.

Author Correction: Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites.

In the version of this Article originally published, the units of the Fig. 3a x axis were incorrectly given as meV. They should have been eV. This has now been corrected in all versions of the Article.

Ultrafast charge carrier dynamics in quantum confined 2D perovskite.

We studied the charge carrier dynamics in 2D perovskite NBT2PbI4 by ultrafast optical pump-THz probe spectroscopy. We observed a few ps long relaxation dynamics that can be ascribed to the band to band carrier recombination, in the absence of any contribution from many-body and trap assisted processes. The transient conductivity spectra show that the polaron dynamics is strongly modulated by the presence of a rich exciton population. The polarization field resulting from the exciton formation acts as the source of a restoring force that localizes polarons. This is revealed by the presence of a negative imaginary conductivity. Our results show that the dynamics of excitons in 2D perovskites at room temperature can be detected by monitoring their effect on the conductivity of the photoinduced polaronic carrier.

Metal Coordination Sphere Deformation Induced Highly Stokes-Shifted, Ultra Broadband Emission in 2D Hybrid Lead-Bromide Perovskites and Investigation of Its Origin.

Published studies of layered (2D) (100)-oriented hybrid lead-bromide perovskites evidence a correlation between increased inter-octahedral (Pb-Br-Pb) distortions and the appearance of broadband white light emission. However, the impact of distortions within their constituent [PbBr6 ]4- octahedra has yet to be assessed. Herein, we report two new (100)-oriented 2D Pb-Br perovskites, whose structures display unusually high intra-octahedral distortions, whilst retaining minimal inter-octahedral distortions. Using a combination of temperature-dependent, power-dependent and time-resolved photoluminescence spectroscopic measurements, we show that increased intra-octahedral distortion induces exciton localization processes and leads to formation of multiple photoinduced emissive colour centres. Ultimately, this leads to highly Stokes-shifted, ultrabroad white light emission at room temperature.

Broadband Emission in Two-Dimensional Hybrid Perovskites: The Role of Structural Deformation.

Only a selected group of two-dimensional (2D) lead-halide perovskites shows a peculiar broad-band photoluminescence. Here we show that the structural distortions of the perovskite lattice can determine the defectivity of the material by modulating the defect formation energies. By selecting and comparing two archetype systems, namely, (NBT)2PbI4 and (EDBE)PbI4 perovskites (NBT = n-butylammonium and EDBE = 2,2-(ethylenedioxy)bis(ethylammonium)), we find that only the latter, subject to larger deformation of the Pb-X bond length and X-Pb-X bond angles, sees the formation of VF color centers whose radiative decay ultimately leads to broadened PL. These findings highlight the importance of structural engineering to control the optoelectronic properties of this class of soft materials.

Lead-Free MA2CuCl(x)Br(4-x) Hybrid Perovskites.

Despite their extremely good performance in solar cells with efficiencies approaching 20% and the emerging application for light-emitting devices, organic-inorganic lead halide perovskites suffer from high content of toxic, polluting, and bioaccumulative Pb, which may eventually hamper their commercialization. Here, we present the synthesis of two-dimensional (2D) Cu-based hybrid perovskites and study their optoelectronic properties to investigate their potential application in solar cells and light-emitting devices, providing a new environmental-friendly alternative to Pb. The series (CH3NH3)2CuCl(x)Br(4-x) was studied in detail, with the role of Cl found to be essential for stabilization. By exploiting the additional Cu d-d transitions and appropriately tuning the Br/Cl ratio, which affects ligand-to-metal charge transfer transitions, the optical absorption in this series of compounds can be extended to the near-infrared for optimal spectral overlap with the solar irradiance. In situ formation of Cu(+) ions was found to be responsible for the green photoluminescence of this material set. Processing conditions for integrating Cu-based perovskites into photovoltaic device architectures, as well as the factors currently limiting photovoltaic performance, are discussed: among them, we identified the combination of low absorption coefficient and heavy mass of the holes as main limitations for the solar cell efficiency. To the best of our knowledge, this is the first demonstration of the potential of 2D copper perovskite as light harvesters and lays the foundation for further development of perovskite based on transition metals as alternative lead-free materials. Appropriate molecular design will be necessary to improve the material's properties and solar cell performance filling the gap with the state-of-the-art Pb-based perovskite devices.

2D Hybrid Perovskites: From Static and Dynamic Structures to Potential Applications.

2D perovskites have received great attention recently due to their structural tunability and environmental stability, making them highly promising candidates for various applications by breaking property bottlenecks that affect established materials. However, in 2D perovskites, the complicated interplay between organic spacers and inorganic slabs makes structural analysis challenging to interpret. A deeper understanding of the structure-property relationship in these systems is urgently needed to enable high-performance tunable optoelectronic devices. Herein, this study examines how structural changes, from constant lattice distortion and variable structural evolution, modeled with both static and dynamic structural descriptors, affect macroscopic properties and ultimately device performance. The effect of chemical composition, crystallographic inhomogeneity, and mechanical-stress-induced static structural changes and corresponding electronic band variations is reported. In addition, the structure dynamics are described from the viewpoint of anharmonic vibrations, which impact electron-phonon coupling and the carriers' dynamic processes. Correlated carrier-matter interactions, known as polarons and acting on fine electronic structures, are then discussed. Finally, reliable guidelines to facilitate design to exploit structural features and rationally achieve breakthroughs in 2D perovskite applications are proposed. This review provides a global structural landscape of 2D perovskites, expected to promote the prosperity of these materials in emerging device applications.

How Photogenerated I2 Induces I-Rich Phase Formation in Lead Mixed Halide Perovskites.

Bandgap tunability of lead mixed halide perovskites (LMHPs) is a crucial characteristic for versatile optoelectronic applications. Nevertheless, LMHPs show the formation of iodide-rich (I-rich) phase under illumination, which destabilizes the semiconductor bandgap and impedes their exploitation. Here, it is shown that how I2 , photogenerated upon charge carrier trapping at iodine interstitials in LMHPs, can promote the formation of I-rich phase. I2 can react with bromide (Br- ) in the perovskite to form a trihalide ion I2 Br- (Iδ- -Iδ+ -Brδ- ), whose negatively charged iodide (Iδ- ) can further exchange with another lattice Br- to form the I-rich phase. Importantly, it is observed that the effectiveness of the process is dependent on the overall stability of the crystalline perovskite structure. Therefore, the bandgap instability in LMHPs is governed by two factors, i.e., the density of native defects leading to I2 production and the Br- binding strength within the crystalline unit. Eventually, this study provides rules for the design of chemical composition in LMHPs to reach their full potential for optoelectronic devices.

Structural effects on the luminescence properties of CsPbI3 nanocrystals.

Metal halide perovskite nanocrystals (NCs) are promising for photovoltaic and light-emitting applications. Due to the softness of their crystal lattice, structural modifications have a critical impact on their optoelectronic properties. Here we investigate the size-dependent optoelectronic properties of CsPbI3 NCs ranging from 7 to 17 nm, employing temperature and pressure as thermodynamic variables to modulate the energetics of the system and selectively tune the interatomic distances. By temperature-dependent photoluminescence spectroscopy, we have found that luminescence quenching channels exhibit increased non-radiative losses and weaker exciton-phonon coupling in bigger particles, in turn affecting the luminescence efficiency. Through pressure-dependent measurements up to 2.5 GPa, supported by XRD characterization, we revealed a NC-size dependent solid-solid phase transition from the γ-phase to the δ-phase. Importantly, the optical response to these structural changes strongly depends on the size of the NC. Our findings provide an interesting guideline to correlate the size and structural and optoelectronic properties of CsPbI3 NCs, important for engineering the functionalities of this class of soft semiconductors.

Plurality of excitons in Ruddlesden-Popper metal halides and the role of the B-site metal cation.

We investigate the effect of metal cation substition on the excitonic structure and dynamics in a prototypical Ruddlesden-Popper metal halide. Through an in-depth spectroscopic and theoretical analysis, we identify the presence of multiple resonances in the optical spectra of a phenethyl ammonium tin iodide, a tin-based RPMH. Based on ab initio calculations, we assign these resonances to distinct exciton series that originate from the splitting of the conduction band due to spin-orbit coupling. While the splitting energy in the tin based system is low enough to enable the observation of the higher lying exciton in the visible-range spectrum of the material, the higher splitting energy in the lead counterpart prevents the emergence of such a feature. We elucidate the critical role played by the higher lying excitonic state in the ultrafast carrier thermalization dynamics.

Many-Exciton Quantum Dynamics in a Ruddlesden-Popper Tin Iodide.

We present a study on the many-body exciton interactions in a Ruddlesden-Popper tin halide, namely, (PEA)2SnI4 (PEA = phenylethylammonium), using coherent two-dimensional electronic spectroscopy. The optical dephasing times of the third-order polarization observed in these systems are determined by exciton many-body interactions and lattice fluctuations. We investigate the excitation-induced dephasing (EID) and observe a significant reduction of the dephasing time with increasing excitation density as compared to its lead counterpart (PEA)2PbI4, which we have previously reported in a separate publication [J. Chem. Phys.2020, 153, 164706]. Surprisingly, we find that the EID interaction parameter is four orders of magnitude higher in (PEA)2SnI4 than that in (PEA)2PbI4. This increase in the EID rate may be due to exciton localization arising from a more statically disordered lattice in the tin derivative. This is supported by the observation of multiple closely spaced exciton states and the broadening of the linewidth with increasing population time (spectral diffusion), which suggests a static disordered structure relative to the highly dynamic lead-halide. Additionally, we find that the exciton nonlinear coherent lineshape shows evidence of a biexcitonic state with low binding energy (<10 meV) not observed in the lead system. We model the lineshapes based on a stochastic scattering theory that accounts for the interaction with a nonstationary population of dark background excitations. Our study provides evidence of differences in the exciton quantum dynamics between tin- and lead-based Ruddlesden-Popper metal halides (RPMHs) and links them to the exciton-exciton interaction strength and the static disorder aspect of the crystalline structure.

A2Bn-1PbnI3n+1 (A = BA, PEA; B = MA; n = 1, 2): Engineering Quantum-Well Crystals for High Mass Density and Fast Scintillators.

Quantum-well (QW) hybrid organic-inorganic perovskite (HOIP) crystals, e.g., A2PbX4 (A = BA, PEA; X = Br, I), demonstrated significant potentials as scintillating materials for wide energy radiation detection compared to their individual three-dimensional (3D) counterparts, e.g., BPbX3 (B = MA). Inserting 3D into QW structures resulted in new structures, namely A2BPb2X7 perovskite crystals, and they may have promising optical and scintillation properties toward higher mass density and fast timing scintillators. In this article, we investigate the crystal structure as well as optical and scintillation properties of iodide-based QW HOIP crystals, A2PbI4 and A2MAPb2I7. A2PbI4 crystals exhibit green and red emission with the fastest PL decay time <1 ns, while A2MAPb2I7 crystals exhibit a high mass density of >3.0 g/cm3 and tunable smaller bandgaps <2.1 eV resulting from quantum and dielectric confinement. We observe that A2PbI4 and PEA2MAPb2I7 show emission under X- and γ-ray excitations. We further observe that some QW HOIP iodide scintillators exhibit shorter radiation absorption lengths (∼3 cm at 511 keV) and faster scintillation decay time components (∼0.5 ns) compared to those of QW HOIP bromide scintillators. Finally, we investigate the light yields of iodide-based QW HOIP crystals at 10 K (∼10 photons/keV), while at room temperature they still show pulse height spectra with light yields between 1 and 2 photons/keV, which is still >5 times lower than those for bromides. The lower light yields can be the drawbacks of iodide-based QW HOIP scintillators, but the promising high mass density and decay time results of our study can provide the right pathway for further improvements toward fast-timing applications.

Self-Powered Edible Defrosting Sensor.

Improper freezing of food causes food waste and negatively impacts the environment. In this work, we propose a device that can detect defrosting events by coupling a temperature-activated galvanic cell with an ionochromic cell, which is activated by the release of ions during current flow. Both the components of the sensor are fabricated through simple and low-energy-consuming procedures from edible materials. The galvanic cell operates with an aqueous electrolyte solution, producing current only at temperatures above the freezing point of the solution. The ionochromic cell exploits the current generated during the defrosting to release tin ions, which form complexes with natural dyes, causing the color change. Therefore, this sensor provides information about defrosting events. The temperature at which the sensor reacts can be tuned between 0 and -50 °C. The device can thus be flexibly used in the supply chain: as a sensor, it can measure the length of exposure to above-the-threshold temperatures, while as a detector, it can provide a signal that there was exposure to above-the-threshold temperatures. Such a device can ensure that frozen food is handled correctly and is safe for consumption. As a sensor, it could be used by the workers in the supply chain, while as a detector, it could be useful for end consumers, ensuring that the food was properly frozen during the whole supply chain.

Lasing in Two-Dimensional Tin Perovskites.

Two-dimensional (2D) perovskites have been proposed as materials capable of improving the stability and surpassing the radiative recombination efficiency of three-dimensional perovskites. However, their luminescent properties have often fallen short of what has been expected. In fact, despite attracting considerable attention for photonic applications during the last two decades, lasing in 2D perovskites remains unclear and under debate. Here, we were able to improve the optical gain properties of 2D perovskite and achieve optically pumped lasing. We show that the choice of the spacer cation affects the defectivity and photostability of the perovskite, which in turn influences its optical gain. Based on our synthetic strategy, we obtain PEA2SnI4 films with high crystallinity and favorable optical properties, resulting in amplified spontaneous emission (ASE) with a low threshold (30 µJ/cm2), a high optical gain above 4000 cm-1 at 77 K, and ASE operation up to room temperature.

Layered Perovskite Doping with Eu3+ and ß-diketonate Eu3+ Complex.

Metal halide perovskites are attracting great interest for the fabrication of light-emitting devices encompassing light-emitting diodes, lasers, and scintillators. As the field develops, perovskite doping emerges as a promising way to enrich the material functionalities and enhance the luminescence yield and tunability. While Mn+2 addition has been well explored, doping with lanthanides has received less attention, even though their intense and line-like luminescence is interesting for a wide range of applications. In this work, we study the doping of NMA2PbBr4 layered perovskites with Eu3+ and Eu3+ tetrakis ß-diketonate complex. By exploiting the antenna effect of the naphthalene-based functional cation (NMA = 1-naphtylmethylammonium), direct sensitization of Eu3+ is obtained; nevertheless, it is not very efficient due to the non-optimal energy level alignment with the resonance acceptor level of the lanthanide. Protection of Eu3+ in the form of tetrakis ß-diketonate complex grants a more ideal coordination geometry and energetic landscape for the energy transfer to europium in the perovskite matrix, allowing for a nearly 30-fold improvement in luminescence yield. This work sets the basis for new synthetic strategies for the design of functional perovskite/lanthanide host-guest systems with improved luminescence properties.

Picosecond Charge Localization Dynamics in CH3NH3PbI3 Perovskite Probed by Infrared-Activated Vibrations.

Hybrid metal halide perovskites exhibit well-defined semiconducting properties and efficient optoelectronic performance considering their soft crystal structure and low-energy lattice motions. The response of such a crystal lattice to light-induced charges is a fundamental question, for which experimental insight into ultrafast time scales is still sought. Here, we use infrared-activated vibrations (IRAV) of the organic components within the hybrid perovskite lattice as a sensitive probe for local structural reorganizations after photoexcitation, with femtosecond resolution. We find that the IRAV signal response shows a delayed rise of about 3 ps and subsequent decay of pronounced monomolecular character, distinguishing it from absorption associated with free carriers. We interpret our results as a two-step carrier localization process. Initially, carriers localize transiently in local energy minima formed by lattice fluctuations. A subpopulation of these can then fall into deeper trapped states over picoseconds, likely due to local reorganization of the organic molecules surrounding the carriers.

All-polymer methylammonium lead iodide perovskite microcavities.

Thanks to a high photoluminescence quantum yield, large charge carrier diffusion, and ease of processing from solution, perovskite materials are becoming increasingly interesting for flexible optoelectronic devices. However, their deposition requires wide range solvents that are incompatible with many other flexible and solution-processable materials, including polymers. Here, we show that methylammonium lead iodide (MAPbI3) films can be directly synthesized on all-polymer microcavities via simple addition of a perfluorinated layer which protects the polymer photonic structure from the perovskite processing solvents. The new processing provides microcavities with a quality factor Q = 155, that is in agreement with calculations and the largest value reported so far for fully solution processed perovskite microcavities. Furthermore, the obtained microcavity shows strong spectral and angular redistribution of the the MAPbI3 photoluminescence spectrum, which shows a 3.5 fold enhanced intensity with respect to the detuned reference. The opportunity to control and modify the emission of a MAPbI3 film via a simple spun-cast polymer structure is of great interest in advanced optoelectronic applications requiring high colour purity or emission directionality.

Brightness Enhancement in Pulsed-Operated Perovskite Light-Emitting Transistors.

Perovskite light-emitting field-effect transistors (PeLEFETs) provide a versatile device architecture to control transport and electroluminescence properties of hybrid perovskites, enabling injection of high charge carrier density and spatial control of the radiative recombination zone. Ionic screening and organic cation polarization effects typical of metal-halide perovskites, however, critically affect PeLEFET efficiency and reliability. In this work, we demonstrate a new device operation mode based on high-frequency modulation of the applied voltages, which allows significant reduction of ionic drift/screening in methylammonium lead iodide light-emitting transistors. In optimized top contact PeLEFETs, AC operation results in brighter and more uniform electroluminescence compared to DC-driven devices, whereas high-frequency modulation enables electroluminescence emission up to room temperature.