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The 2D Ruddlesden-Popper (RP) perovskites Cs 2 PbI 2 Cl 2 (Pb-based, n = 1) and Cs 2 SnI 2 Cl 2 (Sn-based, n = 1) stand out as unique and rare instances of entirely inorganic constituents within the more expansive category of organic/inorganic 2D perovskites. These materials have recently garnered significant attention for their strong UV-light responsiveness, exceptional thermal stability, and theoretically predicted ultrahigh carrier mobility. In this study, we synthesized Pb and Sn-based n = 1 2D RP perovskite films covering millimeter-scale areas for the first time, utilizing a one-step chemical vapor deposition (CVD) method under atmospheric conditions. These films feature perovskite layers oriented horizontally relative to the substrate. Multilayered Cs 3 Pb 2 I 3 Cl 4 (Pb-based, n = 2) and Cs 3 Sn 2 I 3 Cl 4 (Sn-based, n = 2) films were also obtained for the first time, and their crystallographic structures were refined by combining X-ray diffraction (XRD) and density functional theory (DFT) calculations. DFT calculations and experimental optical spectroscopy support band-gap energy shifts related to the perovskite layer thickness. We demonstrate bias-free photodetectors using the Sn-based, n = 1 perovskite with reproducible photocurrent and a fast 84 ms response time. The present work not only demonstrates the growth of high-quality all-inorganic multilayered 2D perovskites via the CVD method but also suggests their potential as promising candidates for future optoelectronic applications.

We present a design strategy for fabricating ultrastable phase-pure films of formamidinium lead iodide (FAPbI 3 ) by lattice templating using specific two-dimensional (2D) perovskites with FA as the cage cation. When a pure FAPbI 3 precursor solution is brought in contact with the 2D perovskite, the black phase forms preferentially at 100°C, much lower than the standard FAPbI 3 annealing temperature of 150°C. X-ray diffraction and optical spectroscopy suggest that the resulting FAPbI 3 film compresses slightly to acquire the (011) interplanar distances of the 2D perovskite seed. The 2D-templated bulk FAPbI 3 films exhibited an efficiency of 24.1% in a p-i-n architecture with 0.5-square centimeter active area and an exceptional durability, retaining 97% of their initial efficiency after 1000 hours under 85°C and maximum power point tracking.

Twisted moiré photonic crystal is an optical analog of twisted graphene or twisted transition metal dichalcogenide bilayers. In this paper, we report the fabrication of twisted moiré photonic crystals and randomized moiré photonic crystals and their use in enhanced extraction of light in light-emitting diodes (LEDs). Fractional diffraction orders from randomized moiré photonic crystals are more uniform than those from moiré photonic crystals. Extraction efficiencies of 76.5%, 77.8% and 79.5% into glass substrate are predicted in simulations of LED patterned with twisted moiré photonic crystals, defect-containing photonic crystals and random moiré photonic crystals, respectively, at 584 nm. Extraction efficiencies of optically pumped LEDs with 2D perovskite (BA) 2 (MA) n -1 Pb n I 3 n +1 of n = 3 and (5-(2'-pyridyl)-tetrazolato)(3-CF 3 -5-(2'-pyridyl)pyrazolato) platinum(II) (PtD) have been measured., (© 2023 IOP Publishing Ltd.)

Three-dimensional (3D) organic-inorganic lead halide perovskites have emerged in the past few years as a promising material for low-cost, high-efficiency optoelectronic devices. Spurred by this recent interest, several subclasses of halide perovskites such as two-dimensional (2D) halide perovskites have begun to play a significant role in advancing the fundamental understanding of the structural, chemical, and physical properties of halide perovskites, which are technologically relevant. While the chemistry of these 2D materials is similar to that of the 3D halide perovskites, their layered structure with a hybrid organic-inorganic interface induces new emergent properties that can significantly or sometimes subtly be important. Synergistic properties can be realized in systems that combine different materials exhibiting different dimensionalities by exploiting their intrinsic compatibility. In many cases, the weaknesses of each material can be alleviated in heteroarchitectures. For example, 3D-2D halide perovskites can demonstrate novel behavior that neither material would be capable of separately. This review describes how the structural differences between 3D halide perovskites and 2D halide perovskites give rise to their disparate materials properties, discusses strategies for realizing mixed-dimensional systems of various architectures through solution-processing techniques, and presents a comprehensive outlook for the use of 3D-2D systems in solar cells. Finally, we investigate applications of 3D-2D systems beyond photovoltaics and offer our perspective on mixed-dimensional perovskite systems as semiconductor materials with unrivaled tunability, efficiency, and technologically relevant durability.

Achieving high solar-to-hydrogen (STH) efficiency concomitant with long-term durability using low-cost, scalable photo-absorbers is a long-standing challenge. Here we report the design and fabrication of a conductive adhesive-barrier (CAB) that translates >99% of photoelectric power to chemical reactions. The CAB enables halide perovskite-based photoelectrochemical cells with two different architectures that exhibit record STH efficiencies. The first, a co-planar photocathode-photoanode architecture, achieved an STH efficiency of 13.4% and 16.3 h to t 60 , solely limited by the hygroscopic hole transport layer in the n-i-p device. The second was formed using a monolithic stacked silicon-perovskite tandem, with a peak STH efficiency of 20.8% and 102 h of continuous operation before t 60 under AM 1.5G illumination. These advances will lead to efficient, durable, and low-cost solar-driven water-splitting technology with multifunctional barriers., (© 2023. The Author(s).)

Interlayer excitons (IXs) in two-dimensional (2D) heterostructures provide an exciting avenue for exploring optoelectronic and valleytronic phenomena. Presently, valleytronic research is limited to transition metal dichalcogenide (TMD) based 2D heterostructure samples, which require strict lattice (mis) match and interlayer twist angle requirements. Here, we explore a 2D heterostructure system with experimental observation of spin-valley layer coupling to realize helicity-resolved IXs, without the requirement of a specific geometric arrangement, i.e., twist angle or specific thermal annealing treatment of the samples in 2D Ruddlesden-Popper (2DRP) halide perovskite/2D TMD heterostructures. Using first-principle calculations, time-resolved and circularly polarized luminescence measurements, we demonstrate that Rashba spin-splitting in 2D perovskites and strongly coupled spin-valley physics in monolayer TMDs render spin-valley-dependent optical selection rules to the IXs. Consequently, a robust valley polarization of ∼14% with a long exciton lifetime of ∼22 ns is obtained in type-II band aligned 2DRP/TMD heterostructure at ∼1.54 eV measured at 80 K. Our work expands the scope for studying spin-valley physics in heterostructures of disparate classes of 2D semiconductors.

Realizing solution-processed heterostructures is a long-enduring challenge in halide perovskites because of solvent incompatibilities that disrupt the underlying layer. By leveraging the solvent dielectric constant and Gutmann donor number, we could grow phase-pure two-dimensional (2D) halide perovskite stacks of the desired composition, thickness, and bandgap onto 3D perovskites without dissolving the underlying substrate. Characterization reveals a 3D-2D transition region of 20 nanometers mainly determined by the roughness of the bottom 3D layer. Thickness dependence of the 2D perovskite layer reveals the anticipated trends for n-i-p and p-i-n architectures, which is consistent with band alignment and carrier transport limits for 2D perovskites. We measured a photovoltaic efficiency of 24.5%, with exceptional stability of T 99 (time required to preserve 99% of initial photovoltaic efficiency) of >2000 hours, implying that the 3D/2D bilayer inherits the intrinsic durability of 2D perovskite without compromising efficiency.

Radiation detectors are widely used in physics, materials science, chemistry, and biology. Halide perovskites are known for their superior properties including tunable bandgaps and chemical compositions, high defect tolerance, solution-processable synthesis of films and crystals, and high carrier diffusion length. Recently, halide perovskites have attracted enormous interest as particle radiation detectors for both charged (α and β) and uncharged (neutrons) particles. Solid-state detectors based on single crystal perovskites can detect α particles and thermal neutrons with energy-resolved spectra. Halide perovskite scintillators are also able to detect β particles and fast neutrons. In this review, we briefly introduce the fundamentals of radiation detection and summarize the recent progress on halide perovskite detectors for particle radiation.

Understanding and tailoring the physical behaviour of halide perovskites under practical environments is critical for designing efficient and durable optoelectronic devices. Here, we report that continuous light illumination leads to >1% contraction in the out-of-plane direction in two-dimensional hybrid perovskites, which is reversible and strongly dependent on the specific superlattice packing. X-ray photoelectron spectroscopy measurements show that constant light illumination results in the accumulation of positive charges in the terminal iodine atoms, thereby enhancing the bonding character of inter-slab I-I interactions across the organic barrier and activating out-of-plane contraction. Correlated charge transport, structural and photovoltaic measurements confirm that the onset of the light-induced contraction is synchronized to a threefold increase in carrier mobility and conductivity, which is consistent with an increase in the electronic band dispersion predicted by first-principles calculations. Flux-dependent space-charge-limited current measurement reveals that light-induced interlayer contraction activates interlayer charge transport. The enhanced charge transport boosts the photovoltaic efficiency of two-dimensional perovskite solar cells up to 18.3% by increasing the device's fill factor and open-circuit voltage., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

Halide perovskites doped with magnetic impurities (such as the transition metals Mn 2+ , Co 2+ , Ni 2+ ) are being explored for a wide range of applications beyond photovoltaics, such as spintronic devices, stable light-emitting diodes, single-photon emitters, and magneto-optical devices. However, despite several recent studies, there is no consensus on whether the doped magnetic ions will predominantly replace the octahedral B-site metal via substitution or reside at interstitial defect sites. Here, by performing correlated nanoscale X-ray microscopy, spatially and temporally resolved photoluminescence measurements, and magnetic force microscopy on the inorganic 2D perovskite Cs 2 PbI 2 Cl 2 , we show that doping Mn 2+ into the structure results in a lattice expansion. The observed lattice expansion contrasts with the predicted contraction expected to arise from the B-site metal substitution, thus implying that Mn 2+ does not replace the Pb 2+ sites. Photoluminescence and electron paramagnetic resonance measurements confirm the presence of Mn 2+ in the lattice, while correlated nano-XRD and X-ray fluorescence track the local strain and chemical composition. Density functional theory calculations predict that Mn 2+ atoms reside at the interstitial sites between two octahedra in the triangle formed by one Cl - and two I - atoms, which results in a locally expanded structure. These measurements show the fate of the transition metal dopants, the local structure, and optical emission when they are doped at dilute concentrations into a wide band gap semiconductor.

We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni 2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous., (© 2021 Wiley-VCH GmbH.)

Light-matter coupling in excitonic materials has been the subject of intense recent investigations due to emergence of new materials. Two-dimensional layered hybrid organic/inorganic perovskites (2D HOIPs) support strongly bound excitons at room temperature with some of the highest oscillator strengths and electric loss tangents among the known excitonic materials. Here, we report strong light-matter coupling in Ruddlesden-Popper phase 2D HOIP crystals without the necessity of an external cavity. We report the concurrent occurrence of multiple orders of hybrid light-matter states via both reflectance and luminescence spectroscopy in thick (>100 nm) crystals and near-unity absorption in thin (<20 nm) crystals. We observe resonances with quality factors of >250 in hybridized exciton-polaritons and identify a linear correlation between exciton-polariton mode splitting and extinction coefficient of the various 2D HOIPs. Our work opens the door to studying polariton dynamics in self-hybridized and open cavity systems with broad applications in optoelectronics and photochemistry.

Photocathodes emit electrons when illuminated, a process utilized across many technologies. Cutting-edge applications require a set of operating conditions that are not met with current photocathode materials. Meanwhile, halide perovskites have been studied extensively and have shown a lot of promise for a wide variety of optoelectronic applications. Well-documented halide perovskite properties such as inexpensive growth techniques, improved carrier mobility, low trap density, and tunable direct band gaps make them promising candidates for next-generation photocathode materials. Here, we use density functional theory to explore the possible application of pure inorganic perovskites (CsPbBr 3 and CsPbI 3 ) as photocathodes. It is determined that the addition of a Cs coating improved the performance by lowering the work function anywhere between 1.5 and 3 eV depending on the material, crystal surface, and surface coverage. A phenomenological model, modified from that developed by Gyftopoulos and Levine, is used to predict the reduction in work function with Cs coverage. The results of this work aim to guide the further experimental development of Cs-coated halide perovskites for photocathode materials.

2D perovskites are a class of halide perovskites offering a pathway for realizing efficient and durable optoelectronic devices. However, the broad chemical phase space and lack of understanding of film formation have led to quasi-2D perovskite films with polydispersity in perovskite layer thicknesses, which have hindered device performance and stability. Here, a simple and scalable approach is reported, termed as the "phase-selective method", to fabricate 2D perovskite thin films with homogenous layer thickness (phase purity). The phase-selective method involves the dissolution of single-crystalline powders with a homogeneous perovskite layer thickness in desired solvents to fabricate thin films. In situ characterizations reveal the presence of sub-micrometer-sized seeds in solution that preserve the memory of the dissolved single crystals and dictate the nucleation and growth of grains with an identical thickness of the perovskite layers in thin films. Photovoltaic devices with a p-i-n architecture are fabricated with such films, which yield an efficiency of 17.1% enabled by an open-circuit voltage of 1.20 V, while preserving 97.5% of their peak performance after 800 h under illumination without any external thermal management., (© 2021 Wiley-VCH GmbH.)

Electron sources are a critical component in a wide range of applications such as electron-beam accelerator facilities, photomultipliers, and image intensifiers for night vision. We report efficient, regenerative and low-cost electron sources based on solution-processed halide perovskites thin films when they are excited with light with energy equal to or above their bandgap. We measure a quantum efficiency up to 2.2% and a lifetime of more than 25 h. Importantly, even after degradation, the electron emission can be completely regenerated to its maximum efficiency by deposition of a monolayer of Cs. The electron emission from halide perovskites can be tuned over the visible and ultraviolet spectrum, and operates at vacuum levels with pressures at least two-orders higher than in state-of-the-art semiconductor electron sources.

Achieving technologically relevant performance and stability for optoelectronics, energy conversion, photonics, spintronics and quantum devices requires creating atomically precise materials with tailored homo- and hetero-interfaces, which can form functional hierarchical assemblies. Nature employs tunable sequence chemistry to create complex architectures, which efficiently transform matter and energy, however, in contrast, the design of synthetic materials and their integration remains a long-standing challenge. Organic-inorganic two-dimensional halide perovskites (2DPKs) are organic and inorganic two-dimensional layers, which self-assemble in solution to form highly ordered periodic stacks. They exhibit a large compositional and structural phase space, which has led to novel and exciting physical properties. In this Review, we discuss the current understanding in the structure and physical properties of 2DPKs from the monolayers to assemblies, and present a comprehensive comparison with conventional semiconductors, thereby providing a broad understanding of low-dimensional semiconductors that feature complex organic-inorganic hetero-interfaces.

Two-dimensional (2D) halide perovskites have great promise in optoelectronic devices because of their stability and optical tunability, but the subtle effects on the inorganic layer when modifying the organic spacer remain unclear. Here, we introduce two homologous series of Ruddlesden-Popper (RP) structures using the branched isobutylammonium (IBA) and isoamylammonium (IAA) cations with the general formula (RA) 2 (MA) n -1 Pb n I 3 n +1 (RA = IBA, IAA; MA = methylammonium n = 1-4). Surprisingly, the IAA n = 2 member results in the first modulated 2D perovskite structure with a ripple with a periodicity of 50.6 Å occurring in the inorganic slab diagonally to the [101] direction of the basic unit cell. This leads to an increase of Pb-I-Pb angles along the direction of the wave. Generally, both series show larger in-plane bond angles resulting from the additional bulkiness of the spacers compensating for the MA's small size. Larger bond angles have been shown to decrease the bandgap which is seen here with the bulkier IBA leading to both larger in-plane angles and lower bandgaps except for n = 2, in which the modulated structure has a lower bandgap because of its larger Pb-I-Pb angles. Photo-response was tested for the n = 4 compounds and confirmed, signaling their potential use in solar cell devices. We made films using an MACl additive which showed good crystallinity and preferred orientation according to grazing-incidence wide-angle scattering (GIWAXS). As exemplar, the two n = 4 samples were employed in devices with champion efficiencies of 8.22% and 7.32% for IBA and IAA, respectively., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The optical and light emission properties of tin and lead halide perovskites are remarkable because of the robust room-temperature (RT) performance, broad wavelength tunability, high efficiency, and good quenching resistance to defects. These highly desirable attributes promise to transform current light-emitting devices, phosphors, and lasers. One disadvantage in most of these materials is the sensitivity to moisture. Here, we report a new air-stable one-dimensional (1D) hybrid lead-free halide material (DAO)Sn 2 I 6 (DAO, 1,8-octyldiammonium) that is resistant to water for more than 15 h. The material exhibits a sharp optical absorption edge at 2.70 eV and a strong broad orange light emission centered at 634 nm, with a full width at half-maximum (fwhm) of 142 nm (0.44 eV). The emission has a long photoluminescence (PL) lifetime of 582 ns, while the intensity is constant over a very broad temperature range (145-415 K) with a photoluminescence quantum yield (PLQY) of at least 20.3% at RT. Above 415 K the material undergoes a structural phase transition from monoclinic ( C 2/ c ) to orthorhombic ( Ibam) accompanied by a red shift in the band gap and a quench in the photoluminescence emission. Density functional theory calculations support the trend in the optical properties and the 1D electronic nature of the structure, where the calculated carrier effective masses along the inorganic chain are significantly lower than those perpendicular to the chain. Thin films of the compound readily fabricated from solutions exhibit the same optical properties, but with improved PLQY of 36%, for a 60 nm thick film, among the highest reported for lead-free low-dimensional 2D and 1D perovskites and metal halides.

Rolston et al suggest through a convective heating scheme that the mechanism of light-induced lattice expansion is from light-induced thermal heating. We bring out key differences in the physical observables that are not discussed and different from what is observed in the original paper by Tsai et al ., (Copyright © 2020, American Association for the Advancement of Science.)

Quasi-two-dimensional (2D) mixed-cation hybrid halide perovskites (A' 2 A N -1 M N X 3 N +1 ; A' = large organic molecule with cationic group, A = [Cs + , CH 3 NH 3 + , HC(NH 2 ) 2 + ], M = [Pb, Sn, Ge], X = [I - , Br - , Cl - ]) have rapidly emerged as candidates to improve the structural stability and device lifetime of 3D perovskite semiconductor devices under operating conditions. The addition of the large A' cation to the traditional AMX 3 structure introduces several synthetic degrees of freedom and breaks M-X bonds, giving rise to peculiar critical phase behavior in the phase space of these complex materials. In this work, we propose a thermodynamic model parametrized by first-principles calculations to generate the phase diagram of 2D and quasi-2D perovskites (q-2DPKs) based on the mechanics and electrostatics of the interface between the A' cations and the metal halide octahedral network. Focusing on the most commonly studied methylammonium lead iodide system where A' is n- butylammonium (BA; CH 3 (CH 2 ) 3 NH 3 + ), we find that the apparent difficulty in synthesizing phase-pure samples with a stoichiometric index N > 5 can be attributed to the energetic competition between repulsion of opposing interfacial dipole layers and mechanical relaxation induced by interfacial stress. Our model shows quantitative agreement with experimental observations of the maximum phase-pure stoichiometric index ( N crit ) and explains the nonmonotonic evolution of the lattice parameters with increasing stoichiometric index ( N ). This model is generalizable to the entire family of q-2DPKs and can guide the design of photovoltaic and optical materials that combine the structural stability of the q-2DPKs while retaining the charge carrier properties of their 3D counterparts.

Nickel oxide (NiO) is a commonly used contact material for a variety of thin-film optoelectronic technologies based on organic or hybrid materials. In such setups, interfaces play a crucial role as they can reduce, if not kill, the device performances by bringing additional traps or energy barriers, hindering the extraction of charge carriers from the active layer. Here, we computationally examine a prototype halide perovskite architecture, NiO/MAPbI 3 (MA = CH 3 NH 3 + ), that has shown excellent photovoltaic performance and, in particular, a large open-circuit voltage. We show that efficient hole collection is achieved only when considering the role of vacancies induced by standard material deposition techniques. Specifically, Ni vacancies lead to nearly perfect valence band energy level alignment between the active layer and the contact material. Finally, we show how Li doping greatly improves the performances of the device and further propose alternative dopants. Our results suggest the high tunability of NiO interfaces for the design of optimized optoelectronic devices far beyond that of halide perovskites.

Two-dimensional layered halide organic perovskites (LHOPs) are promising candidates for many optoelectronic applications due to their interesting tunable properties. They provide a unique opportunity to control energy and charge dynamics via the independent tunability of the energy levels within the perovskite and the organic spacer for various optoelectronic applications. In the perovskite layer alone, one can replace the Pb (Sn), the halide (X = I, Br, Cl), the organic component, and the number of layers between the organic spacer layers. In addition, there are many possibilities for organic spacer layers between the perovskite layers, making it difficult for experimental methods to comprehensively explore such an extensive combinatorial space. Of particular technological interest is alignment of electronic levels between the perovskite layer and the organic spacer layer, leading to desired transfer of energy or charge carriers between perovskite and organic components. For example, as band edge absorption is almost entirely attributed to the perovskite layer, one way to demonstrate energy transfer is to observe triplet emission from organic spacers. State-of-the-art computational chemistry tools can be used to predict the properties of many stoichiometries in search for LHOPs that have the most promising electronic-structure features. In this first-principles study, we survey a group of π-conjugated organic spacer candidates for use in triplet light-emitting LHOPs. Utilizing density functional theory (DFT) and time-dependent DFT, we calculate the first singlet (S 1 ) and triplet (T 1 ) excitation energy in the ground-state geometry and the first triplet excitation energy in the excited-triplet-state relaxed geometry (T 1 * ). By comparing these energies to the known lowest exciton energy level of Pb n X 3 n +1 perovskite layers (X = I, Br, Cl), we can identify organic spacer and perovskite layer pairings for possible transfer of Wannier excitons from the inorganic perovskite lattice to spin-triplet Frenkel excitons located on the organic cation. We successfully identify ten organic spacer candidates for possible pairing with perovskite layers of specific halide composition to achieve triplet light emission across the visible energy range. Molecular dynamics simulations predict that finite temperatures and perovskite environment have little influence on the average excitation energies of the two common organic spacers naphthylethylammonium (NEA) and phenelethylammonium (PEA). We find significant thermal broadening up to 0.5 eV of the optical excitation energies appearing due to finite temperature effects. The findings herein provide insights into alignment of electronic levels of the conjugated organic spacer with the layer.

Atomically thin crystals of transition metal dichalcogenides (TMDs) host excitons with strong binding energies and sizable light-matter interactions. Coupled to optical cavities, monolayer TMDs routinely reach the regime of strong light-matter coupling, where excitons and photons admix coherently to form polaritons up to room temperature. Here, we explore the two-dimensional nature of TMD polaritons with scanning-cavity hyperspectral imaging. We record a spatial map of polariton properties of extended WS 2 monolayers coupled to a tunable micro cavity in the strong coupling regime, and correlate it with maps of exciton extinction and fluorescence taken from the same flake with the cavity. We find a high level of homogeneity, and show that polariton splitting variations are correlated with intrinsic exciton properties such as oscillator strength and linewidth. Moreover, we observe a deviation from thermal equilibrium in the resonant polariton population, which we ascribe to non-Markovian polariton-phonon coupling. Our measurements reveal a promisingly consistent polariton landscape, and highlight the importance of phonons for future polaritonic devices.

Monolayer transition metal dichalcogenides integrated in optical microcavities host exciton-polaritons as a hallmark of the strong light-matter coupling regime. Analogous concepts for hybrid light-matter systems employing spatially indirect excitons with a permanent electric dipole moment in heterobilayer crystals promise realizations of exciton-polariton gases and condensates with inherent dipolar interactions. Here, we implement cavity-control of interlayer excitons in vertical MoSe 2 -WSe 2 heterostructures. Our experiments demonstrate the Purcell effect for heterobilayer emission in cavity-modified photonic environments, and quantify the light-matter coupling strength of interlayer excitons. The results will facilitate further developments of dipolar exciton-polariton gases and condensates in hybrid cavity - van der Waals heterostructure systems.

Transition metal dichalcogenides (TMDCs) and two-dimensional organic and inorganic hybrid lead halide perovskites (2DPVSKs) have emerged as highly promising materials for ultralight and ultrathin optoelectronics application. They both exhibit tunability of electronic properties such as band structure, and they can form heterostructures with various types of two-dimensional materials for novel physical properties not observed in single components. However, TMDCs exhibit poor emission efficiency due to defect states and direct-to-indirect interband transition, and 2DPVSKs suffer from poor stability in ambient atmosphere. Here we report that fabrication of TMDC-on-2DPVSK heterostructures using a solvent-free process leads to novel optical transitions unique to the heterostructure which arise from the hybrid interface and exhibit a strong photoluminescence. Moreover, a two orders of magnitude enhancement of the photoluminescence as compared to WS 2 emission is observed. The TMDC on top of 2DPVSK also significantly improves the stability as compared to bare 2DPVSK. Enhanced emission can be explained by electronic structure modification of TMDC by novel interfacial interactions between TMDC and 2DPVSK materials, which shows promise of the heterostructure for high efficiency and stable optoelectronic devices.

Two-dimensional (2D) hybrid halide perovskites are promising in optoelectronic applications, particularly solar cells and light-emitting devices (LEDs), and for their increased stability as compared to 3D perovskites. Here, we report a new series of structures using propylammonium (PA + ), which results in a series of Ruddlesden-Popper (RP) structures with the formula (PA) 2 (MA) n -1 Pb n I 3 n +1 ( n = 3, 4) and a new homologous series of "step-like" (SL) structures where the PbI 6 octahedra connect in a corner- and face-sharing motif with the general formula (PA) 2 m +4 (MA) m -2 Pb 2 m +1 I 7 m +4 ( m = 2, 3, 4). The RP structures show a blue-shift in bandgap for decreasing n (1.90 eV for n = 4 and 2.03 eV for n = 3), while the SL structures have an even greater blue-shift (2.53 eV for m = 4, 2.74 eV for m = 3, and 2.93 eV for m = 2). DFT calculations show that, while the RP structures are electronically 2D quantum wells, the SL structures are electronically 1D quantum wires with chains of corner-sharing octahedra "insulated" by blocks of face-sharing octahedra. Dark measurements for RP crystals show high resistivity perpendicular to the layers (10 11 Ω cm) but a lower resistivity parallel to them (10 7 Ω cm). The SL crystals have varying resistivity in all three directions, confirming both RP and SL crystals' utility as anisotropic electronic materials. The RP structures show strong photoresponse, whereas the SL materials exhibit resistivity trends that are dominated by ionic transport and no photoresponse. Solar cells were made with n = 3 giving an efficiency of 7.04% (average 6.28 ± 0.65%) with negligible hysteresis.

Recently, mixed-cation perovskites have promised enhanced performances concerning stability and efficiency in optoelectronic devices. Here, we report a systematic study on the effects of cation alloying on polaronic properties in cation-alloyed perovskites using first principle calculations. We find that cation alloying significantly reduces the polaron binding energies for both electrons and holes compared to pure methylammonium lead iodide (MAPbI 3 ). This is rationalized in terms of crystal symmetry reduction that causes polarons to be more delocalized. Electron polarons undergo large Jahn-Teller distortions (∼15-30%), whereas hole polarons tend to shrink the lattice by ∼5%. Such different lattice distortion footprints could be utilized to distinguish the type of polarons. Finally, our simulations show that Cs, formamidinium (FA), and MA mixtures can effectively minimize polaron binding energy while weakly affecting band gap, in a good agreement with experimental findings. These modeling results can guide future development of halide perovskite materials compositions for optoelectronic applications.

The unique hybrid nature of 2D Ruddlesden-Popper (R-P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R-P perovskites, by utilizing pentylamine (PA) 2 (MA) n-1 Pb n I 3 n+1 ( n = 1-5, PA = CH 3 (CH 2 ) 4 NH 3 + , C5) and hexylamine (HA) 2 (MA) n-1 Pb n I 3 n+1 ( n = 1-4, HA = CH 3 (CH 2 ) 5 NH 3 + , C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R-P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20-80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.

(4NPEA) 2 PbI 4 (4NPEA = 4-nitrophenylethylammonium) is the first 3 × 3 corrugated 2D organic-Pb/I perovskite. The nitro groups are involved in cation-cation and cation-iodide interactions. The structure contains both highly distorted and near-ideal PbI 6 octahedra, consistent with the observation of two 207 Pb NMR resonances, while the optical properties resemble those of other 2D perovskites with distorted PbI 6 octahedra.

In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A') 2 (A) n -1 M n X 3 n +1 [where A = Cs + , CH 3 NH 3 + , HC(NH 2 ) 2 + ; A' = ammonium cation acting as spacer; M = Ge 2+ , Sn 2+ , Pb 2+ ; and X = Cl - , Br - , I - ] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members ( n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure-function relationships. We report the effective synthesis of the highest iodide n -members yet, namely (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 5 Pb 6 I 19 ( n = 6) and (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 6 Pb 7 I 22 ( n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for "(CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 8 Pb 9 I 28 " (" n = 9"). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (Δ H f ), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n -dependent solar cell efficiency in the range of 9-12.6% in these higher n -members, highlighting the strong promise of these materials for high-performance devices., Competing Interests: The authors declare no conflict of interest.

Halide perovskites have demonstrated remarkable performance in optoelectronic applications. Despite extraordinary progress, questions remain about device stability. We report an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies of several experimentally relevant halide perovskites using isolated clusters. Local lattice symmetry, electronic structure, and electron-phonon coupling are interrelated in polaron formation in these materials. To illustrate this, first-principles calculations are performed on (MA/Cs/FA)Pb(I/Br) 3 and MASnI 3 . Across the materials studied, electron small polaron formation is manifested by Jahn-Teller-like distortions in the central octahedron, with apical PbI bonds expanding significantly more than the equatorial bonds. In contrast, hole polarons cause the central octahedron to uniformly contract. This difference in manifestation of electron and hole polaron formation can be a tool to determine what is taking place in individual systems to systematically control performance. Other trends as the anion and cations are changed are established for optimization in specific optoelectronic applications.

Low-dimensional halide perovskites have recently attracted intense interest as alternatives to the three-dimensional (3D) perovskites because of their greater tunability and higher environmental stability. Herein, we present the new homologous 2D series (NH 3 C m H 2 m NH 3 )(CH 3 NH 3 ) n-1 Pb n I 3 n+1 ( m = 4-9; n = 1-4), where m represents the carbon-chain number and n equals layer-thickness number. Multilayer ( n > 1) 2D perovskites incorporating diammonium cations were successfully synthesized by the solid-state grinding method for m = 4 and 6 and by the solution method for m = 7-9. Structural characterization by single-crystal X-ray diffraction for the m = 8 and m = 9 series ( n = 1-4) reveals that these compounds adopt the Cc space group for even n members and Pc for odd n members. The optical bandgaps are 2.15 eV for two-layer ( n = 2), 2.01 eV for three-layer ( n = 3), and 1.90 eV for four-layer ( n = 4). The materials exhibit excellent solution processability, and casting thin-films of the n = 3 members was successfully accomplished. The films show a clear tendency for the higher- m members to have preferred orientation on the glass substrate, with m = 8 exhibiting almost perfect vertical layer orientation and m = 9 displaying both vertical and parallel layer orientation, as confirmed by grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The vertical layer orientation for the (NH 3 C 8 H 16 NH 3 )(CH 3 NH 3 ) 2 Pb 3 I 10 member results in the best thermal, light, and air stability within this series, thus showing excellent potential for solar cell applications.

Surface states are ubiquitous to semiconductors and significantly impact the physical properties and, consequently, the performance of optoelectronic devices. Moreover, surface effects are strongly amplified in lower dimensional systems such as quantum wells and nanostructures. Layered halide perovskites (LHPs) are two-dimensional solution-processed natural quantum wells where optoelectronic properties can be tuned by varying the perovskite layer thickness n, i.e., the number of octahedra spanning the layer. They are efficient semiconductors with technologically relevant stability. Here, a generic elastic model and electronic structure modeling are applied to LHPs heterostructures with various layer thickness. We show that the relaxation of the interface strain is triggered by perovskite layers above a critical thickness. This leads to the release of the mechanical energy arising from the lattice mismatch, which nucleates the surface reorganization and may potentially induce the formation of previously observed lower energy edge states. These states, which are absent in three-dimensional perovskites are anticipated to play a crucial role in the design of LHPs for optoelectronic systems.

During the past decades, major advances have been made in both the generation and detection of infrared light; however, its efficient wavefront manipulation and information processing still encounter great challenges. Efficient and fast optoelectronic modulators and spatial light modulators are required for mid-infrared imaging, sensing, security screening, communication and navigation, to name a few. However, their development remains elusive, and prevailing methods reported so far have suffered from drawbacks that significantly limit their practical applications. In this study, by leveraging graphene and metasurfaces, we demonstrate a high-performance free-space mid-infrared modulator operating at gigahertz speeds, low gate voltage and room temperature. We further pixelate the hybrid graphene metasurface to form a prototype spatial light modulator for high frame rate single-pixel imaging, suggesting orders of magnitude improvement over conventional liquid crystal or micromirror-based spatial light modulators. This work opens up the possibility of exploring wavefront engineering for infrared technologies for which fast temporal and spatial modulations are indispensable., Competing Interests: The authors declare that they have no conflict of interest.

Ruddlesden-Popper halide perovskites are 2D solution-processed quantum wells with a general formula A 2 A' n-1 M n X 3n+1 , where optoelectronic properties can be tuned by varying the perovskite layer thickness (n-value), and have recently emerged as efficient semiconductors with technologically relevant stability. However, fundamental questions concerning the nature of optical resonances (excitons or free carriers) and the exciton reduced mass, and their scaling with quantum well thickness, which are critical for designing efficient optoelectronic devices, remain unresolved. Here, using optical spectroscopy and 60-Tesla magneto-absorption supported by modeling, we unambiguously demonstrate that the optical resonances arise from tightly bound excitons with both exciton reduced masses and binding energies decreasing, respectively, from 0.221 m 0 to 0.186 m 0 and from 470 meV to 125 meV with increasing thickness from n equals 1 to 5. Based on this study we propose a general scaling law to determine the binding energy of excitons in perovskite quantum wells of any layer thickness.

State-of-the-art quantum-well-based devices such as photovoltaics, photodetectors, and light-emission devices are enabled by understanding the nature and the exact mechanism of electronic charge transport. Ruddlesden-Popper phase halide perovskites are two-dimensional solution-processed quantum wells and have recently emerged as highly efficient semiconductors for solar cell approaching 14% in power conversion efficiency. However, further improvements will require an understanding of the charge transport mechanisms, which are currently unknown and further complicated by the presence of strongly bound excitons. Here, we unambiguously determine that dominant photocurrent collection is through electric field-assisted electron-hole pair separation and transport across the potential barriers. This is revealed by in-depth device characterization, coupled with comprehensive device modeling, which can self-consistently reproduce our experimental findings. These findings establish the fundamental guidelines for the molecular and device design for layered 2D perovskite-based photovoltaics and optoelectronic devices, and are relevant for other similar quantum-confined systems.

Ruddlesden-Popper reduced-dimensional hybrid perovskite (RDP) semiconductors have attracted significant attention recently due to their promising stability and excellent optoelectronic properties. Here, the RDP crystallization mechanism in real time from liquid precursors to the solid film is investigated, and how the phase transition kinetics influences phase purity, quantum well orientation, and photovoltaic performance is revealed. An important template-induced nucleation and growth of the desired (BA) 2 (MA) 3 Pb 4 I 13 phase, which is achieved only via direct crystallization without formation of intermediate phases, is observed. As such, the thermodynamically preferred perpendicular crystal orientation and high phase purity are obtained. At low temperature, the formation of intermediate phases, including PbI 2 crystals and solvate complexes, slows down intercalation of ions and increases nucleation barrier, leading to formation of multiple RDP phases and orientation randomness. These insights enable to obtain high quality (BA) 2 (MA) 3 Pb 4 I 13 films with preferentially perpendicular quantum well orientation, high phase purity, smooth film surface, and improved optoelectronic properties. The resulting devices exhibit high power conversion efficiency of 12.17%. This work should help guide the perovskite community to better control Ruddlesden-Popper perovskite structure and further improve optoelectronic and solar cell devices., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Layered hybrid organic-inorganic perovskites (HOPs) have re-emerged as potential technological solutions for next-generation photovoltaic and optoelectronic applications. Their two-dimensional (2D) nature confers them a significant flexibility and results in the appearance of quantum and dielectric confinements. Such confinements are at the origin of their fascinating properties, and understanding them from a fundamental level is of paramount importance for optimization. Here, we provide an in-depth investigation of band alignments of 2D HOP allowing access to carriers' confinement potentials. 2D HOPs are conceptualized as composite materials in which pseudoinorganic and -organic components are defined. In this way, computational modeling of band alignments becomes affordable using first-principles methods. First, we show that the composite approach is suitable to study the position-dependent dielectric profiles and enables clear differentiation of the respective contributions of inorganic and organic components. Then we apply the composite approach to a variety of 2D HOPs, assessing the impact on the confinement potentials of well and barrier thickness, of the nature of the inorganic well, and of structural transitions. Using the deduced potentials, we further discuss the limitations of the effective mass approximation, scrutinizing the electronic properties of this family of composite materials. Our simulations demonstrate type-I dominant band alignment in 2D HOPs. Finally, we outline design principles on band alignment toward achieving specific optoelectronic properties. Thus, we present alternative theoretical methods to inspect the properties of 2D hybrid perovskites and expect that the composite approach will be applicable to other classes of layered materials.

Light-induced structural dynamics plays a vital role in the physical properties, device performance, and stability of hybrid perovskite-based optoelectronic devices. We report that continuous light illumination leads to a uniform lattice expansion in hybrid perovskite thin films, which is critical for obtaining high-efficiency photovoltaic devices. Correlated, in situ structural and device characterizations reveal that light-induced lattice expansion benefits the performances of a mixed-cation pure-halide planar device, boosting the power conversion efficiency from 18.5 to 20.5%. The lattice expansion leads to the relaxation of local lattice strain, which lowers the energetic barriers at the perovskite-contact interfaces, thus improving the open circuit voltage and fill factor. The light-induced lattice expansion did not compromise the stability of these high-efficiency photovoltaic devices under continuous operation at full-spectrum 1-sun (100 milliwatts per square centimeter) illumination for more than 1500 hours., (Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Hybrid perovskites are on a trajectory toward realizing the most efficient single-junction, solution-processed photovoltaic devices. However, a critical issue is the limited understanding of the correlation between the degree of crystallinity and the emergent perovskite/hole (or electron) transport layer on device performance and photostability. Here, the controlled growth of hybrid perovskites on nickel oxide (NiO) is shown, resulting in the formation of thin films with enhanced crystallinity with characteristic peak width and splitting reminiscent of the tetragonal phase in single crystals. Photophysical and interface sensitive measurements reveal a reduced trap density at the perovskite/NiO interface in comparison with perovskites grown on poly(3,4-ethylene dioxy thiophene) polystyrene sulfonate. Photovoltaic cells exhibit a high open circuit voltage (1.12 V), indicating a near-ideal energy band alignment. Moreover, photostability of photovoltaic devices up to 10-Suns is observed, which is a direct result of the superior crystallinity of perovskite thin films on NiO. These results elucidate the critical role of the quality of the perovskite/hole transport layer interface in rendering high-performance and photostable optoelectronic devices., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

State-of-the-art light-emitting diodes (LEDs) are made from high-purity alloys of III-V semiconductors, but high fabrication cost has limited their widespread use for large area solid-state lighting. Here, efficient and stable LEDs processed from solution with tunable color enabled by using phase-pure 2D Ruddlesden-Popper (RP) halide perovskites with a formula (CH 3 (CH 2 ) 3 NH 3 ) 2 (CH 3 NH 3 ) n -1 Pb n I 3 n +1 are reported. By using vertically oriented thin films that facilitate efficient charge injection and transport, efficient electroluminescence with a radiance of 35 W Sr -1 cm -2 at 744 nm with an ultralow turn-on voltage of 1 V is obtained. Finally, operational stability tests suggest that phase purity is strongly correlated to stability. Phase-pure 2D perovskites exhibit >14 h of stable operation at peak operating conditions with no droop at current densities of several Amperes cm -2 in comparison to mixtures of 2D/3D or 3D perovskites, which degrade within minutes., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report a detailed investigation on Raman spectroscopy in vapor-phase chalcogenization grown, high-quality single-crystal atomically thin molybdenum diselenide samples. Measurements were performed in samples with four different incident laser excitation energies ranging from 1.95 eV ⩽ E ex ⩽ 2.71 eV, revealing rich spectral information in samples ranging from N = 1-4 layers and a thick, bulk sample. In addition to previously observed (and identified) peaks, we specifically investigate the origin of a peak near ω ≈ 250 cm -1 . Our density functional theory and Bethe-Salpeter calculations suggest that this peak arises from a double-resonant Raman process involving the ZA acoustic phonon perpendicular to the layer. This mode appears prominently in freshly prepared samples and disappears in aged samples, thereby offering a method for ascertaining the high optoelectronic quality of freshly prepared 2D-MoSe 2 crystals. We further present an in-depth investigation of the energy-dependent variation of the position of this and other peaks and provide evidence of C-exciton-phonon coupling in monolayer MoSe 2 . Finally, we show how the signature peak positions and intensities vary as a function of layer thickness in these samples.

Organic photovoltaic donor-acceptor junction devices composed of π-conjugated polymer electron donors (D) and fullerene electron acceptors (A) show greatly increased performance when a spacer material is inserted between the two layers (W. Y. Nie, G. Gupta, B. K. Crone, F. L. Liu, D. L. Smith, P. P. Ruden, C. Y. Kuo, H. Tsai, H. L. Wang, H. Li, S. Tretiak and A. D. Mohite, Adv. Sci., 2015, 2, 1500024.). For instance, experimental results reveal significant improvement of photocurrent when a terthiophene oligomer derivative is inserted in between π-conjugated poly(3-hexylthiophene-2,5-diyl) (P3HT) donor and C 60 acceptor. These results indicate favorable charge separation dynamics, which is addressed by our present joint theoretical/experimental study establishing the beneficial alignment of electronic levels due to the specific morphology of the material. Namely, based on the experimental data we have constructed extended structural interface models containing C 60 fullerenes and P3HT separated by aligned oligomer chains. Our time-dependent density functional theory (TD-DFT) calculations based on a long-range corrected functional, allowed us to address the energetics of essential electronic states and analyze them in terms of charge transfer (CT) character. Specifically, the simulations reveal the electronic spectra composed of a ladder of excited states evolving excitation toward spatial charge separation: an initial excitonic excitation at P3HT decomposes into charges by sequentially relaxing through bands of C 60 -centric, oligomer → C 60 and P3HT → C 60 CT states. Our modeling exposes a critical role of dielectric environment effects and electronic couplings in the self-assembled spacer oligomer layer on the energetics of critical CT states leading to a reduced back-electron transfer, preventing recombination losses, and thus rationalizes physical processes underpinning experimental observations.

We present the new homologous series (C(NH 2 ) 3 )(CH 3 NH 3 ) n Pb n I 3n+1 (n = 1, 2, 3) of layered 2D perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden-Popper (RP) 2D perovskites, the ACI perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterparts with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: E g = 2.27 eV for n = 1 to E g = 1.99 eV for n = 2 and E g = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP perovskites. First-principles theoretical electronic structure calculations confirm the experimental optical gap trends suggesting that the ACI perovskites are direct bandgap semiconductors with wide valence and conduction bandwidths. To assess the potential of the ACI perovskites toward solar cell applications, we studied the (C(NH 2 ) 3 )(CH 3 NH 3 ) 3 Pb 3 I 10 (n = 3) compound. Compact thin films from the (C(NH 2 ) 3 )(CH 3 NH 3 ) 3 Pb 3 I 10 compound with excellent surface coverage can be obtained from the antisolvent dripping method. Planar photovoltaic devices from optimized ACI perovskite films yield a power-conversion-efficiency of 7.26% with a high open-circuit voltage of ∼1 V and a striking fill factor of ∼80%.

It is one of the most important needs to develop renewable, scalable and multifunctional methods for the fabrication of 3D carbon architectures. Even though a lot of methods have been developed to create porous and mechanically stable 3D scaffolds, the fabrication and control over the synthesis of such architectures still remain a challenge. Here, we used Magnetospirillum magneticum (AMB-1) bacteria as a bio-template to fabricate light-weight 3D solid structure of carbon nanotubes (CNTs) with interconnected porosity. The resulting porous scaffold showed good mechanical stability and large surface area because of the excellent pore interconnection and high porosity. Steered molecular dynamics simulations were used to quantify the interactions between nanotubes and AMB-1 via the cell surface protein MSP-1 and flagellin. The 3D CNTs-AMB1 nanocomposite scaffold is further demonstrated as a potential substrate for electrodes in supercapacitor applications.

The values of the ionization energies of transition metal dichalcogenides (TMDs) are needed to assess their potential usefulness in semiconductor heterojunctions for high-performance optoelectronics. Here, we report on the systematic determination of ionization energies for three prototypical TMD monolayers (MoSe 2 , WS 2 , and MoS 2 ) on SiO 2 using photoemission electron microscopy with deep ultraviolet illumination. The ionization energy displays a progressive decrease from MoS 2 , to WS 2 , to MoSe 2 , in agreement with predictions of density functional theory calculations. Combined with the measured energy positions of the valence band edge at the Brillouin zone center, we deduce that, in the absence of interlayer coupling, a vertical heterojunction comprising any of the three TMD monolayers would form a staggered (type-II) band alignment. This band alignment could give rise to long-lived interlayer excitons that are potentially useful for valleytronics or efficient electron-hole separation in photovoltaics.

Transition metal dichalcogenide semiconductors represent elementary components of layered heterostructures for emergent technologies beyond conventional optoelectronics. In their monolayer form they host electrons with quantized circular motion and associated valley polarization and valley coherence as key elements of opto-valleytronic functionality. Here, we introduce two-dimensional polarimetry as means of direct imaging of the valley pseudospin degree of freedom in monolayer transition metal dichalcogenides. Using MoS 2 as a representative material with valley-selective optical transitions, we establish quantitative image analysis for polarimetric maps of extended crystals, and identify valley polarization and valley coherence as sensitive probes of crystalline disorder. Moreover, we find site-dependent thermal and non-thermal regimes of valley-polarized excitons in perpendicular magnetic fields. Finally, we demonstrate the potential of wide-field polarimetry for rapid inspection of opto-valleytronic devices based on atomically thin semiconductors and heterostructures.

A key challenge in photovoltaics today is to develop cell technologies with both higher efficiencies and lower fabrication costs than incumbent crystalline silicon (c-Si) single-junction cells. While tandem cells have higher efficiencies than c-Si alone, it is generally challenging to find a low-cost, high-performance material to pair with c-Si. However, the recent emergence of 22% efficient perovskite photovoltaics has created a tremendous opportunity for high-performance, low-cost perovskite / crystalline silicon tandem photovoltaic cells. Nonetheless, two key challenges remain. First, integrating perovskites into tandem structures has not yet been demonstrated to yield performance exceeding commercially available crystalline silicon modules. Second, the stability of perovskites is inconsistent with the needs of most end-users, who install photovoltaic modules to produce power for 25 years or more. Making these cells viable thus requires innovation in materials processing, device design, fabrication, and yield. We will address these two gaps in the photovoltaic literature by investigating new types of 2D perovskite materials with n-butylammonium spacer layers, and integrating these materials into bifacial tandem solar cells providing at least 30% normalized power production. We find that an optimized 2D perovskite ((BA) 2 (MA) 3 (Sn 0.6 Pb 0.4 ) 4 I 13 )/silicon bifacial tandem cell, given a globally average albedo of 30%, yields a normalized power production of 30.31%, which should be stable for extended time periods without further change in materials or encapsulation.