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The small exciton binding energy of perovskite suggests that the long-lived photoluminescence and slow recovery of the ground state bleaching of the tetragonal phase at room temperature results primarily from the decay of free charges rather than the decay of the initially created excitons. Here we demonstrate the ground state bleaching recovery of the orthorhombic phase of methylammonium lead iodide (CH3NH3PbI3) is much faster than that of the tetragonal phase using temperature dependent transient absorption spectroscopy. The distribution in orientation of the methylammonium group which is disordered in the tetragonal phase and ordered in the orthorhombic phase results in smaller dielectric constant and larger exciton binding energy in the latter phase. We observe the recovery of the ground state bleaching in the orthorhombic phase to be comprised of decays of both excitons and free charges. Our findings suggest CH3NH3PbI3 behaves like a nonexcitonic semiconductor in the tetragonal phase and an excitonic semiconductor in the orthorhombic phase. (Figure Presented).

Improving charge insertion into intercalation hosts is essential for crucial energy and memory technologies. The layered material TiS 2 provides a promising template for study, but further development of this compound demands improvement to its ion kinetics. Here, we report the incorporation of Se atoms into TiS 2 nanobelts to address barriers related to sluggish ion motion in the material. TiS 1.8 Se 0.2 nanobelts are synthesized through a solid-state method, and structural and electrochemical characterizations reveal that solid solutions based on TiS 1.8 Se 0.2 nanobelts display increased interlayer spacing and electrical conductivity compared to pure TiS 2 nanobelts. Cyclic voltammetry and electrochemical impedance spectroscopy indicate that the capacitive behavior of the TiS 2 electrode is improved upon Se incorporation, particularly at low depths of discharge in the materials. The presence of Se in the structure can be directly related to an increased pseudocapacitive contribution to electrode behavior at a low Li + content in the material and thus to improved ion kinetics in the TiS 1.8 Se 0.2 nanobelts., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Self-doping is a particular doping method that has been applied to a wide range of organic semiconductors. However, there is a lack of understanding regarding the relationship between dopant structure and function. A structurally diverse series of self-n-doped perylene diimides (PDIs) is investigated to study the impact of steric encumbrance, counterion selection, and dopant/PDI tether distance on functional parameters such as doping, stability, morphology, and charge-carrier mobility. The studies show that self-n-doping is best enabled by the use of sterically encumbered ammoniums with short tethers and Lewis basic counterions. Additionally, water is found to inhibit doping, which concludes that thermal degradation is merely a phenomenological feature of certain dopants, and that residual solvent evaporation is the primary driver of thermally activated doping. In situ grazing-incidence wide-angle X-ray scattering studies show that sample annealing increases the π-π stacking distance and shrinks grain boundaries for improved long-range ordering. These features are then correlated to contactless carrier-mobility measurements with time-resolved microwave conductivity before and after thermal annealing. The collective relationships between structural features and functionality are finally used to establish explicit self-n-dopant design principles for the future design of materials with improved functionality., (© 2022 Wiley-VCH GmbH.)

Self-doping is an essential method of increasing carrier concentrations in organic electronics that eliminates the need to tailor host-dopant miscibility, a necessary step when employing molecular dopants. Self-n-doping can be accomplished using amines or ammonium counterions as an electron source, which are being incorporated into an ever-increasingly diverse range of organic materials spanning many applications. Self-n-doped materials have demonstrated exemplary and, in many cases, benchmark performances in a variety of applications. However, an in-depth review of the method is lacking. Perylene diimide (PDI) chromophores are an important mainstay in the semiconductor literature with well-known structure-function characteristics and are also one of the most widely utilized scaffolds for self-n-doping. In this review, we describe the unique properties of self-n-doped PDIs, delineate structure-function relationships, and discuss self-n-doped PDI performance in a range of applications. In particular, the impact of amine/ammonium incorporation into the PDI scaffold on doping efficiency is reviewed with regard to attachment mode, tether distance, counterion selection, and steric encumbrance. Self-n-doped PDIs are a unique set of PDI structural derivatives whose properties are amenable to a broad range of applications such as biochemistry, solar energy conversion, thermoelectric modules, batteries, and photocatalysis. Finally, we discuss challenges and the future outlook of self-n-doping principles.

Perylene diimides (PDIs) have garnered attention as organic photocatalysts in recent years for their ability to drive challenging synthetic transformations, such as aryl halide reduction and olefin iodoperfluoroalkylation. Previous work in this area employs spectator pendant groups attached to the imide nitrogen positions of PDIs that are only added to impart solubility. In this work, we employ electron-rich ammonium iodide or ammonium hydroxide pendant groups capable of self-n-doping the PDI core to form radical anions ( R •- ) and dianions ( D ••2- ). We observe R •- formation is favored at low concentrations where aliphatic linkers are able to freely rotate, while D ••2- formation is favored at elevated concentrations likely due to Coulombic stabilization between adjacent chromophores in a similar manner to that of Kasha exciton stabilization. Cyclic voltammetric measurements are consistent with steric encumbrance increasing the Lewis basicity of anions through Coulombic destabilization. However, sterics also inhibit dianion formation by disrupting aggregation. Finally, femtosecond transient absorption measurements reveal that low wavelength excitation (400 nm) preferentially favors the excitation of R •- to the strongly reducing doublet excited state 2 [ R •- ]*. In contrast, higher wavelength excitation (520 nm) favors the formation of the singlet excited state 1 [ N ]*. These findings highlight the importance of dopant architecture, counterion selection, excitation wavelength, and concentration on R •- and D ••2- formation, which has substantial implications for future photocatalytic applications. We anticipate these findings will enable more efficient systems based on self-n-doped PDIs., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The Rashba splitting in hybrid organic-inorganic lead-halide perovskites (HOIP) is particularly promising and yet controversial, due to questions surrounding the presence or absence of inversion symmetry. Here we utilize two-photon absorption spectroscopy to study inversion symmetry breaking in different phases of these materials. This is an all-optical technique to observe and quantify the Rashba effect as it probes the bulk of the materials. In particular, we measure two-photon excitation spectra of the photoluminescence in 2D, 3D, and anionic mixed HOIP crystals, and show that an additional band above, but close to the optical gap is the signature of new two-photon transition channels that originate from the Rashba splitting. The inversion symmetry breaking is believed to arise from ionic impurities that induce local electric fields. The observation of the Rashba splitting in the bulk of HOIP has significant implications for the understanding of their spintronic and optoelectronic device properties., (© 2022. The Author(s).)

Negative emissions technologies will play a critical role in limiting global warming to sustainable levels. Electrocatalytic and/or photocatalytic CO 2 reduction will likely play an important role in this field moving forward, but efficient, selective catalyst materials are needed to enable the widespread adoption of these processes. The rational design of such materials is highly challenging, however, due to the complexity of the reactions involved as well as the large number of structural variables which can influence behavior at heterogeneous interfaces. Currently, there is a significant disconnect between the complexity of materials systems that can be handled experimentally and those that can be modeled theoretically with appropriate rigor and bridging these gaps would greatly accelerate advancements in the field of Negative Emissions Science (NES). Here, we present a perspective on how these gaps between materials design/synthesis, characterization, and theory can be resolved, enabling the rational development of improved materials for CO 2 conversion and other NES applications., (© 2021 The Authors.)

At the very heart of the global semiconductor industry lies the omnipresent push for new materials discovery. New materials constantly rise and fall out of fashion in the scientific literature, with those passing an initial phase of research scrutiny becoming hotbeds of characterization and optimization efforts. Yet, innumerable hours of painstaking research have been devoted to materials that have ultimately fallen by the wayside after crossing over an indefinable threshold, whereupon historical optimism is met with newfound skepticism. Materials have to perform well, and they have to do it quickly. In the past decade, metal-halide perovskites (MHPs) have garnered widespread attention. The hegemonic view in both academic and industrial circles is that these materials could be engineered to meet the demands of the semiconductor industry. Their promise as inexpensive solar cell devices is highly attractive, and it has been nothing short of remarkable that efficiencies have risen from 3.8% in 2009 to more than 25.5% in 2021. Moreover, MHPs are poised to be revolutionary materials in more ways than one. The highest MHP LED efficiency was recently reported (23.4%), and MHPs have demonstrated promise in photodetectors, memristors, and transistors. However, the many excellent properties of MHPs are contrasted by longstanding stability and reproducibility limitations that have hindered their commercialization. Overcoming the limitations of MHPs is ultimately a materials engineering problem, which should be solved by mapping more precise relationships between structure, composition, and device performance. In 1958, Francis Crick famously developed the central dogma of molecular biology which describes the unidirectional flow of information in biological systems. In the words of Crick, "nature has devised a unique instrument in which an underlying simplicity is used to express great subtlety and versatility." In this Account, taking inspiration from the hierarchical organization of nature, we describe a hierarchical approach to materials engineering of organic metal-halide semiconductors. We demonstrate that organo-metal halide semiconductors' dimensionality, composition, and morphology dictate their optoelectronic properties and can be exploited in defining more explicit relationships between structure and function. Here, we traverse three-dimensional (3D), two-dimensional (2D), and one-dimensional (1D) organo-metal halide semiconductors, detailing the morphological and compositional differences in each and the implications that can be drawn within each domain on the engineering process. Control over ion migration pathways via morphology engineering as well as control over charge formation in organic-inorganic semiconductors is demonstrated. Fundamental insights into the amount of static and dynamic disorder in the MHP lattice are provided, which can be continuously tuned as a function of composition and morphology. Using electroabsorption spectroscopy on 2D MHPs, a disorder-induced dipole moment in the exciton proportional to the summed value of static and dynamic disorder is measured. Spectroscopic isolation of exciton features in 2D MHP electroabsorption spectra allows us to obtain precise, model-independent measurements of exciton binding energies to study the effect of chemical substitutions, such as Sn 2+ → Pb 2+ , on the value of the exciton binding energy. Finally, we conclude that this multidimensional platform, with the aid of machine learning and robotics, will be foundational in accurately predicting structure-property-device relationships in organo-metal halide semiconductors in the future.

Solution-processable two-dimensional (2D) organic-inorganic hybrid perovskite (OIHP) quantum wells naturally self-assemble through weak van der Waals forces. In this study, we investigate the structural and optoelectronic properties of 2D-layered butylammonium (C 4 H 9 NH 3 + , BA + ) methylammonium (CH 3 NH 3 + , MA) lead iodide, (BA) 2 (MA) n -1 Pb n I 3 n +1 quantum wells with varying n from 1 to 4. Through conventional structural characterization, (BA) 2 (MA) n -1 Pb n I 3 n +1 thin films showcase high-quality phase ( n ) purity. However, while investigating the optoelectronic properties, it is clear that these van der Waals heterostructures consist of multiple quantum well thicknesses coexisting within a single thin film. We utilized electroabsorption spectroscopy and Liptay theory to develop an analytical tool capable of deconvoluting the excitonic features that arise from different quantum well thicknesses (n) in (BA) 2 (MA) n -1 Pb n I 3 n +1 thin films. To obtain a quantitative assessment of exciton heterogeneities within a thin film comprising multiple quantum well structures, exciton resonances quantified by absorption spectroscopy were modeled as Gaussian features to yield various theory-generated electroabsorption spectra, which were then fit to our experimental electroabsorption features. In addition to identifying the quantum well heterostructures present within a thin film, this novel analytical tool provides powerful insights into the exact exciton composition and can be utilized to analyze the optoelectronic properties of many other mixed-phase quantum well heterostructures beyond those formed by OIHPs. Our findings may help in designing more efficient and reproducible light-emitting diodes based on 2D mixed-phase metal-organic multiple quantum wells.

The sparse selection of available cathode materials that allow for reversible intercalation (deintercalation) of Al 3+ species represents a major hurdle in the development of efficient Al-ion batteries. Herein, we developed cathodes based on TiS 2 nanobelts that are capable of withstanding the high charge density of Al-ion species with minimal host lattice/ion interactions. The fabricated TiS 2 nanobelts are highly anisotropic and are directly grown on a carbon current collector yielding a spatially controlled array. The sum of evidence presented in this work indicates that one-dimensional TiS 2 nanobelt arrays can reversibly accommodate an unprecedented amount of Al ion species within their layered structure with no significant volume expansion as well as full retention of the nanobelt morphology. Thus, the one-dimensional morphology, nanoscale dimensions, short ion diffusion paths, high electrical conductivity, and absence of additives that hinder ion migration lead to Al-based TiS 2 electrochemical devices exhibiting high specific capacity, less capacity fade, and resilience under higher cycling rates at both room temperature and elevated temperatures when compared to TiS 2 platelets. We also present the effects of sulfur vacancies on the electrochemical performance of Al-based TiS 2- x nanobelt array batteries. Although Al-ion batteries are still in their infancy, we believe our TiS 2 nanobelt array cathode insertion hosts may play an important role in addressing the poor kinetics of solid-state Al-ion diffusion to enable efficient alternatives beyond lithium energy storage devices.

We studied spin dynamics of charge carriers in the superlattice-like Ruddlesden-Popper hybrid lead iodide perovskite semiconductors, 2D (BA) 2 (MA)Pb 2 I 7 (with MA = CH 3 NH 3 , and BA = CH 3 (CH 2 ) 3 NH 3 ), and 3D MAPbI 3 using the magnetic field effect (MFE) on conductivity and electroluminescence in their light emitting diodes (LEDs) at cryogenic temperatures. The semiconductors with distinct structural/bulk inversion symmetry breaking, when combined with colossal intrinsic spin-orbit coupling (SOC), theoretically give rise to giant Rashba-type SOC. We found that the magneto-conductance (MC) magnitude increases monotonically with the emission intensity and saturates at ≈0.05% and 0.11% for the MAPbI 3 and (BA) 2 (MA)Pb 2 I 7 , respectively. The magneto-electroluminescence (MEL) response with similar line shapes as the MC response has a significantly larger magnitude, and essentially stays constant at ≈0.22% and ≈0.20% for MAPbI 3 and (BA) 2 (MA)Pb 2 I 7 , respectively. The sign and magnitude of the MC and MEL responses can be quantitatively explained in the framework of the Δg-based excitonic model using rate equations. Remarkably, the width of the MEL response in those materials linearly increases with increasing the applied electric field, where the Rashba coefficient in (BA) 2 (MA)Pb 2 I 7 is estimated to be about 7 times larger than that in MAPbI 3 . Our studies might have significant impact on future development of electrically-controlled spin logic devices via Rashba-like effects.

Methylammonium lead halide perovskite-based solar cells have demonstrated efficiencies as high as 24.2 %, highlighting their potential as inexpensive and solution-processable alternatives to silicon solar cell technologies. Poor stability towards moisture, ultraviolet irradiation, heat, and a bias voltage of the perovskite layer and its various device interfaces limits the commercial feasibility of this material for outdoor applications. Herein, we investigate the role of hydrogen bonding interactions induced when metal halide perovskite crystals are crosslinked with alkyl or π-conjugated boronic acid small molecules (-B(OH) 2 ). The crosslinked perovskite crystals are investigated under continuous light irradiation and moisture exposure. These studies demonstrate that the origin of the interaction between the alkyl or π-conjugated crosslinking molecules is due to hydrogen bonding between the -B(OH) 2 terminal group of the crosslinker and the I of the [PbI 6 ] 4- octahedra of the perovskite layer. Also, this interaction influences the stability of the perovskite layer towards moisture and ultraviolet light irradiation. Morphology and structural analyses, as well as IR studies as a function of aging under both dark and light conditions show that π-conjugated boronic acid molecules are more effective crosslinkers of the perovskite crystals than their alkyl counterparts thus imparting better stability towards light and moisture degradation., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two-dimensional (2D) organic-inorganic hybrid perovskite multiple quantum wells that consist of multilayers of alternate organic and inorganic layers exhibit large exciton binding energies of order of 0.3 eV due to the dielectric confinement between the inorganic and organic layers. We have investigated the exciton characteristics of 2D butylammonium lead iodide, (C 4 H 9 NH 3 ) 2 PbI 4 using photoluminescence and UV-vis absorption in the temperature range of 10 K to 300 K, and electroabsorption spectroscopy. The evolution of an additional absorption/emission at low temperature indicates that this compound undergoes a phase transition at ≈250 K. We found that the electroabsorption spectrum of each structural phase contains contributions from both quantum confined exciton Stark effect and Franz-Keldysh oscillation of the continuum band, from which we could determine more accurately the 1s exciton, continuum band edge, and the exciton binding energy.

Methylammonium lead iodide (CH3NH3PbI3) hybrid perovskite in the tetragonal and orthorhombic phases have different exciton binding energies and demonstrate different excitation kinetics. Here, we explore the role that crystal structure plays in the kinetics via fluence dependent transient absorption spectroscopy. We observe stronger saturation of the free carrier concentration under high pump energy density in the orthorhombic phase relative to the tetragonal phase. We attribute this phenomenon to small dielectric constant, large exciton binding energy, and weak Coulomb screening, which results in difficult exciton dissociation under high light intensity in the orthorhombic phase. At higher excitation intensities, we observe a coherent phonon with an oscillation frequency of 23.4 cm(-1) at 77 K, whose amplitude tracks the increase of the first-order lifetime.

We designed and synthesized a series of isoindigo-based derivatives to investigate how chemical structure modification at both the 6,6'- and 5,5'-positions of the core with electron-rich and electron-poor moieties affect photophysical and redox properties as well as their solid-state organization. Our studies reveal that 6,6'-substitution on the isoindigo core results in a stronger intramolecular charge transfer band due to strong electronic coupling between the 6,6'-substituent and the core, whereas 5,5'-substitution induces a weaker CT band that is more sensitive to the electronic nature of the substituents. In the solid state, 6,6'-derivatives generally form J-aggregates, whereas 5,5'-derivatives form H-aggregates. With only two branched ethylhexyl side chains, the 6,6'-derivatives form organized lamellar structures in the solid state. The incorporation of electron-rich benzothiophene, BT, substituents further enhances ordering, likely because of strong intermolecular donor-acceptor interactions between the BT substituent and the electron-poor isoindigo core on neighboring compounds. Collectively, the enhanced photophysical properties and solid-state organization of the 6,6'-benzothiophene substituted isoindigo derivative compared to the other isoindigo derivatives examined in this study resulted in solar cells with higher power conversion efficiencies when blended with a fullerene derivative.

This investigation focuses on the formation of nanoscale puddles of an intermediate metallic phase (IMP) in the metal-insulator transition (MIT) temperature regime of single-crystalline vanadium dioxide (VO2) nanowires. The electronic structure of VO2 nanowires was examined with scanning tunneling spectroscopy. The evolution of the local density of states of individual nanowires throughout the MIT regime is presented with differential tunneling conductance spectra and images measured as the temperature was increased. Our results show that the formation of an IMP plays an important role in the MIT of intrinsic VO2.

Efficient out-of-plane charge transport is required in vertical device architectures, such as organic solar cells and organic light emitting diodes. Here, we show that graphene, transferred onto different technologically-relevant substrates, can be used to induce face-on molecular stacking and improve out-of-plane hole transport in copper phthalocyanine thin films.