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Two-dimensional hybrid organic-inorganic perovskite (HOIP) semiconductors with pronounced spin splitting, mediated by strong spin-orbit coupling and inversion symmetry breaking, offer the potential for spin manipulation in future spintronic applications. However, HOIPs exhibiting significant conduction/valence band splitting are still relatively rare, given the generally observed preference for (near)centrosymmetric inorganic (especially lead-iodide-based) sublattices, and few approaches are available to control this symmetry breaking within a given HOIP. Here, we demonstrate, using (S-2-MeBA)

The lecture focuses on emerging chalcogenide-based thin-film photovoltaics and provides both an overview of selected absorber candidates that are of recent interest, and a deeper dive into an exemplary Cu2BaSn(S,Se)4-related family.

Following the 2nd release of the “Emerging PV reports,” the best achievements in the performance of emerging photovoltaic devices in diverse emerging photovoltaic research subjects are summarized, as reported in peer‐reviewed articles in academic journals since August 2021. Updated graphs, tables, and analyses are provided with several performance parameters, e.g., power conversion efficiency, open‐circuit voltage, short‐circuit current density, fill factor, light utilization efficiency, and stability test energy yield. These parameters are presented as a function of the photovoltaic bandgap energy and the average visible transmittance for each technology and application, and are put into perspective using, e.g., the detailed balance efficiency limit. The 3rd installment of the “Emerging PV reports” extends the scope toward triple junction solar cells.

We report 2D hybrid perovskites comprising a blend of chiral arylammonium and achiral alkylammonium spacer cations (1:1 mole ratio). These new perovskites feature an unprecedented combination of chirality and alkyl-aryl functionality alongside noncovalent intermolecular interactions (e.g., CH···π interactions), determined by their crystal structures. The mixed-cation perovskites exhibit a circular dichroism that is markedly different from the purely chiral cation analogues, offering new avenues to tune the chiroptical properties of known chiral perovskites, instead of solely relying on otherwise complex chemical syntheses of new useable chiral cations. Further, the ability to dilute the density of chiral cations by mixing with achiral cations may offer a potential way to tailor the spin-based properties in 2D hybrid perovskites, such as Rashba-Dresselhaus spin splitting and chirality-induced spin selectivity and magnetization effects.

Toward suppressing the formation of anti-site defects and related defect clusters in kesterite Cu2ZnSnS4–xSex (CZTS) absorber films, Cu2–II–IV–X4 (II = Sr, Ba; IV = Ge, Sn; X = S, Se) compounds hav...

Two-dimensional (2D) hybrid metal halide perovskites have emerged as outstanding optoelectronic materials and are potential hosts of Rashba/Dresselhaus spin-splitting for spin-selective transport and spin-orbitronics. However, a quantitative microscopic understanding of what controls the spin-splitting magnitude is generally lacking. Through crystallographic and first-principles studies on a broad array of chiral and achiral 2D perovskites, we demonstrate that a specific bond angle disparity connected with asymmetric tilting distortions of the metal halide octahedra breaks local inversion symmetry and strongly correlates with computed spin-splitting. This distortion metric can serve as a crystallographic descriptor for rapid discovery of potential candidate materials with strong spin-splitting. Our work establishes that, rather than the global space group, local inorganic layer distortions induced via appropriate organic cations provide a key design objective to achieve strong spin-splitting in perovskites. New chiral perovskites reported here couple a sizeable spin-splitting with chiral degrees of freedom and offer a unique paradigm of potential interest for spintronics., Two-dimensional hybrid perovskites exhibiting Rashba/Dresselhaus spin-splitting can be potentially used for spin-selective transport and spin-orbitronics, yet the structural determinants of spin-splitting are not well-understood. Here, the authors reveal a specific inorganic layer distortion that correlates with bulk spin-splitting in these materials.

Quaternary chalcogenide materials have long been a source of semiconductors for optoelectronic applications. Recent studies on I2-II-IV-X4 (I = Ag, Cu, Li; II = Ba, Sr, Eu, Pb; IV = Si, Ge, Sn; X = S, Se) materials have shown particular versatility and promise among these compounds. These semiconductors take advantage of a diverse bonding scheme and chemical differences among cations to target a degree of antisite defect resistance. Within this set of compounds, the materials containing both Ag and Sr have not been experimentally studied and leave a gap in the full understanding of the family. Here, we have synthesized powders and single crystals of two Ag- and Sr-containing compounds, Ag2SrSiS4 and Ag2SrGeS4, each found to form in the tetragonal I42m structure of Ag2BaGeS4. During the synthesis targeting the title compounds, two additional materials, Ag2Sr3Si2S8 and Ag2Sr3Ge2S8, have also been identified. These cubic compounds represent impurity phases during the synthesis of Ag2SrSiS4 and Ag2SrGeS4. We show through hybrid density functional theory calculations that Ag2SrSiS4 and Ag2SrGeS4 have highly dispersive band-edge states and indirect band gaps, experimentally measured as 2.08(1) and 1.73(2) eV, respectively. Second-harmonic generation measurements on Ag2SrSiS4 and Ag2SrGeS4 powders show frequency-doubling capabilities in the near-infrared range.

Two-dimensional (2D) hybrid organic-inorganic perovskites consisting of alternating organic and inorganic layers are a new class of layered structures. They have attracted increasing interest for photovoltaic, optoelectronic, and thermoelectric applications, where knowing their thermal transport properties is critical. We carry out both experimental and computational studies on thermal transport properties of 2D butylammonium lead iodide crystals and find their thermal conductivity is ultralow (below 0.3 W m-1 K-1) with very weak anisotropy (around 1.5) among layered crystals. Further analysis reveals that the unique structure with the preferential alignment of organic chains and complicated energy landscape leads to moderately smaller phonon lifetimes in the out-of-plane direction and comparable phonon group velocities in in-plane and out-of-plane directions. These new findings may guide the future design of novel hybrid materials with desired thermal conductivity for various applications.

Electrical doping (that is, intentional engineering of carrier density) underlies most energy-related and optoelectronic semiconductor technologies. However, for the intensely studied halide perovskite family of semiconductors, reliable doping remains challenging, owing to, for example, compensation from and facile migration of intrinsic defects. In this Review, we first discuss the underlying fundamentals of semiconductor doping and then investigate different doping strategies in halide perovskites, including intrinsic defect, extrinsic defect and charge transfer doping, from an experimental as well as a theoretical perspective. We outline the advantages and pitfalls of different characterization techniques to assess doping and examine the impact of doping on optoelectronic properties. Finally, we highlight challenges that need to be overcome to gain control over the electronic properties of this important material class. Halide perovskites exhibit outstanding semiconductor properties and are a key component of a variety of devices, including solar cells and light-emitting diodes. This Review discusses electrical doping strategies for halide perovskites and takes a critical look at the challenges that need to be overcome to control the electronic properties of these semiconducting materials.

Cu2BaSn(S,Se)4 (CBTSSe) has been proposed as an alternative to Cu2ZnSn(S,Se)4 (CZTSSe) for solar absorbers due to its reduced propensity for antisite disorder and band tailing while maintaining the...

Electronic technologies critically rely on the ability to broadly dope the active semiconductor; yet the promising class of halide perovskite semiconductors so far does not allow for significant control over carrier type (p- or n-) and density. The molecular doping approach offers important opportunities for generating free carriers through charge transfer. In this work, we demonstrate effective p-doping of MAPb0.5Sn0.5I3 films using the molecular dopant F4TCNQ as a grain boundary coating, offering a conductivity and hole density tuning range of up to five orders of magnitude, associated with a 190 meV Fermi level down-shift. While charge transfer between MAPb0.5Sn0.5I3 and F4TCNQ appears efficient, dopant ionization decreases with increasing Pb content, highlighting the need for appropriate energy offset between host and dopant molecule. Finally, we show that electrical p-doping impacts the perovskite optoelectronic properties, with a hole recombination lifetime increase of over one order of magnitude, suggesting passivation of deep traps.

Hybrid perovskite solar cells are considered a promising choice for next-generation thin-film photovoltaic technology. To meet commercialization requirements, more research efforts have now been fo...

Significance The main hurdle that prevents earth-abundant iron-based complexes from replacing environmentally unfriendly and expensive heavy metal [e.g., Ru(II), Os(II), Ir(III)] complexes in solar-energy conversion applications is the typical ultrashort (femtosecond timescale) charge-transfer state lifetime of Fe(II) chromophores. We provide a design roadmap to a generation of efficient iron-based photosensitizers and present an Fe(II) complex archetype, FeNHCPZn, which features a profoundly extended metal-to-ligand charge-transfer (3MLCT) lifetime and a large transition-dipole moment difference between its ground and metal-to-ligand charge-transfer states. This supermolecular design promotes superior visible photon harvesting over classic metal complexes while assuring a triplet excited-state oxidation potential appropriate for charge injection into the conduction bands of common semiconductor electrode materials, highlighting its photosensitizing utility in dye-sensitized solar-cell architectures., Exploiting earth-abundant iron-based metal complexes as high-performance photosensitizers demands long-lived electronically excited metal-to-ligand charge-transfer (MLCT) states, but these species suffer typically from femtosecond timescale charge-transfer (CT)-state quenching by low-lying nonreactive metal-centered (MC) states. Here, we engineer supermolecular Fe(II) chromophores based on the bis(tridentate-ligand)metal(II)-ethyne-(porphinato)zinc(II) conjugated framework, previously shown to give rise to highly delocalized low-lying 3MLCT states for other Group VIII metal (Ru, Os) complexes. Electronic spectral, potentiometric, and ultrafast pump–probe transient dynamical data demonstrate that a combination of a strong σ-donating tridentate ligand and a (porphinato)zinc(II) moiety with low-lying π*-energy levels, sufficiently destabilize MC states and stabilize supermolecular MLCT states to realize Fe(II) complexes that express 3MLCT state photophysics reminiscent of their heavy-metal analogs. The resulting Fe(II) chromophore archetype, FeNHCPZn, features a highly polarized CT state having a profoundly extended 3MLCT lifetime (160 ps), 3MLCT phosphorescence, and ambient environment stability. Density functional and domain-based local pair natural orbital coupled cluster [DLPNO-CCSD(T)] theory reveal triplet-state wavefunction spatial distributions consistent with electronic spectroscopic and excited-state dynamical data, further underscoring the dramatic Fe metal-to-extended ligand CT character of electronically excited FeNHCPZn. This design further prompts intense panchromatic absorptivity via redistributing high-energy absorptive oscillator strength throughout the visible spectral domain, while maintaining a substantial excited-state oxidation potential for wide-ranging photochemistry––highlighted by the ability of FeNHCPZn to photoinject charges into a SnO2/FTO electrode in a dye-sensitized solar cell (DSSC) architecture. Concepts enumerated herein afford opportunities for replacing traditional rare-metal–based emitters for solar-energy conversion and photoluminescence applications.

Though CH3NH3PbBr3 single crystals are frequently applied in various optoelectronic devices due to their favorable cuboid geometry, superior optoelectronic properties, and better stability than CH3NH3PbI3, CH3NH3PbBr3 polycrystalline films normally show poorer morphology with scattered crystals than their iodide counterparts, inherently due to their different crystallization habits. In this work, a facile process based on a hot methylamine-based precursor with high viscosity and concentration is demonstrated to counteract rapid ion diffusion. The precursor also has special features including a large colloidal size, a solid form at room temperature, and fast crystallization offered by the easy evacuation of methylamine. CH3NH3PbBr3 films composed of tightly aligned CH3NH3PbBr3 cuboids on micron scale are obtained. Wide channel (100 μm) photodetectors made from the CH3NH3PbBr3 films show promising photoresponse and fast response speeds on par with those based on single crystals, suggesting high film quality and good optoelectronic connections between neighboring cuboids.

Recent work on quaternary semiconductors Cu2BaSn(S,Se)4 and Ag2BaSnSe4 for photovoltaic and thermoelectric applications, respectively, has shown the promise of exploring the broader family of defec...

In a quest for Pb-free perovskites suitable for solar energy applications, Cs2TiBr6 has recently been reported as a promising compound, with appropriate optical and electrical properties as well as high stability under environmental stresses. In this study, we pursue investigation on this compound, demonstrating phase pure Cs2TiBr6 powder formation using solution synthesis and providing complementary experimental characterization and theoretical calculations. An experimental absorption onset of around 2.0 eV is extracted and a weak broad photoluminescence is measured. Density functional theory calculations predict an indirect bandgap, parity-forbidden for both the direct and indirect transitions, which explains the weak and Stokes shifted luminescence. Additionally, we highlight the strong instability of Cs2TiBr6 powder in ambient atmosphere. Therefore, our experimental results supported by theoretical calculations differ from previous results and raise doubts on the suitability of Cs2TiBr6 in its pristine form for solar energy applications.

Fair and meaningful device per- formance comparison among luminescent solar concentrator- photovoltaic (LSC-PV) reports cannot be realized without a gen- eral consensus on reporting stan- dards in LSC-PV research. There- fore, it is imperative to adopt standardized characterization protocols for these emerging types of PV devices that are consistent with other PV devices. This commentary highlights several common limitations in LSC literature and summarizes the best practices moving for- ward to harmonize with standard PV reporting, considering the greater nuances present with LSC-PV. Based on these prac- tices, a checklist of actionable items is provided to help stan- dardize the characterization/re- porting protocols and offer a set of baseline expectations for au- thors, reviewers, and editors. The general consensus combined with the checklist will ultimately guide LSC-PV research towards reliable and meaningful ad- vances.

Quaternary chalcogenide materials have long been a source of semiconductors for optoelectronic applications. Recent studies on I

Hybrid organic–inorganic lead halide perovskites have shown promising results as active layers in light-emitting diodes, typically utilizing the near-monochromatic, free exciton emission. Some perovskite compounds, however, show broad-band emission that is more intense than the free exciton counterpart. In this study, we show that the light emission properties of Ruddlesden–Popper hybrid perovskites PEA2MAn–1PbnI3n+1 (PEA = phenethylammonium, MA = methylammonium) can be tuned by Sn alloying and are highly sensitive to Sn %. With increasing dimensionality, the broad-band emission quantum yield decreases drastically, from 23% in n = 1 to

The fundamental parameters of majority and minority charge carriers—including their type, density and mobility—govern the performance of semiconductor devices yet can be difficult to measure. Although the Hall measurement technique is currently the standard for extracting the properties of majority carriers, those of minority carriers have typically only been accessible through the application of separate techniques. Here we demonstrate an extension to the classic Hall measurement—a carrier-resolved photo-Hall technique—that enables us to simultaneously obtain the mobility and concentration of both majority and minority carriers, as well as the recombination lifetime, diffusion length and recombination coefficient. This is enabled by advances in a.c.-field Hall measurement using a rotating parallel dipole line system and an equation, ΔμH = d(σ2H)/dσ, which relates the hole–electron Hall mobility difference (ΔμH), the conductivity (σ) and the Hall coefficient (H). We apply this technique to various solar absorbers—including high-performance lead-iodide-based perovskites—and demonstrate simultaneous access to majority and minority carrier parameters and map the results against varying light intensities. This information, which is buried within the photo-Hall measurement1,2, had remained inaccessible since the original discovery of the Hall effect in 18793. The simultaneous measurement of majority and minority carriers should have broad applications, including in photovoltaics and other optoelectronic devices. A carrier-resolved photo-Hall technique is developed to extract properties of both majority and minority carriers simultaneously and determine the critical parameters of semiconductor materials under light illumination.

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) represent diverse quantum well heterostructures composed of alternating inorganic and organic layers. While 2D HOIPs are nominally periodic in three dimensions for X-ray scattering, the inorganic layers can orient quasi-randomly, leading to rotational stacking disorder (RSD). RSD manifests as poorly resolved, diffuse X-ray scattering along the stacking direction, limiting the structural description to an apparently disordered subcell. However, local ordering preferences can still exist between adjacent unit cells and can considerably impact the properties, particularly the electronic structure. Here, we elucidate RSD and determine the preferred local ordering in the 2D [AE2T]PbI4 HOIP (AE2T: 5,5′-bis(ethylammonium)-[2,2′-bithiophene]). We use first-principles calculations to determine energy differences between a set of systematically generated supercells with different order patterns. We show that interlayer ordering tendencies are weak, explaining the observed RSD in terms of differing in-plane rotation of PbI6 octahedra in neighboring inorganic planes. In contrast, the ordering preference within a given organic layer is strong, favoring a herringbone-type arrangement of adjacent AE2T cations. The calculated electronic level alignments of proximal organic and inorganic frontier orbitals in the valence band vary significantly with the local arrangement of AE2T cations; only the most stable AE2T configuration leads to an interfacial type-Ib band alignment consistent with observed optical properties. The present study underscores the importance of resolving local structure arrangements in 2D HOIPs for reliable structure-property prediction. (Less)

Although hybrid halide perovskite solar cells (PSCs) have recently reached record efficiency among thin film photovoltaic technologies, the stability of these devices remains a pressing problem for...

Summary Perovskite photovoltaics has achieved rapid development largely due to the spin-coating technique with antisolvent steps at laboratory scale. However, the spin-coating/antisolvent technique limits the device dimension due to film uniformity issues. Up to now, it has been challenging to obtain perovskite devices with high efficiency (e.g., >20%) using scalable methods without antisolvent steps. Herein, an air-blading process is demonstrated to assemble the entire perovskite devices completely free from the spin-coating techniques. This method can coat perovskite precursor on substrates and simultaneously induce nucleation in perovskite intermediate films without any antisolvent steps, leading to highly uniform films. The fully air-bladed perovskite photovoltaics shows the best efficiency (reverse scanning) of >20% for 0.09 cm2 illumination-exposure area and the best efficiency of >19% for 1.0 cm2 illumination-exposure area with high reproducibility (stabilized efficiencies are 19.3% and 18.2%, respectively). Such an air-blading process offers a wide processing window for versatile high-performance perovskite optoelectronics toward large-scale production.

Hybrid perovskites incorporating conjugated organic cations enable unusual charge carrier interactions among organic and inorganic structural components, but are difficult to prepare as films due to disparate component chemical/physical characteristics (e.g., solubility, thermal stability). Here we demonstrate that resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) mitigates these challenges, enabling facile deposition of lead-halide-based perovskite films incorporating variable-length oligothiophene cations. Density functional theory (DFT) predicts suitable organic and inorganic moieties that form quantum-well-like structures with targeted luminescence or exciton separation/quenching. RIR-MAPLE-deposited films enable confirmation of these predictions by optical measurements, which further display excited state behavior transcending traditional quantum-well models—i.e., with appropriate selection of specially synthesized organic/inorganic moieties, intercomponent carrier transfer efficiently converts excitons from singlet to triplet states in organics for which intersystem crossing cannot ordinarily compete with recombination. These observations demonstrate the uniquely versatile excited-state behavior in hybrid perovskite quantum wells, and the value of integrating DFT, organic synthesis, RIR-MAPLE and spectroscopy for screening/preparing rationally devised complex structures.

Non-toxic and air-stable silver bismuth iodide semiconductors are promising light absorber candidates for photovoltaic applications owing to a suitable band gap for multi- or single-junction solar cells. Recently, solution-based film fabrication approaches for several silver bismuth iodide stoichiometries have been investigated. The current work reports on a facile and reproducible two-step coevaporation/annealing approach to deposit compact and pinhole-free films of AgBi2I7, AgBiI4 and Ag2BiI5. X-ray diffraction (XRD) in combination with scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX) analysis reveals formation of pure cubic (Fdm) phase AgBi2I7, cubic (Fdm) or rhombohedra (Rm) phase AgBiI4, each with >3 μm average grain size, or the rhombohedral phase (Rm) Ag2BiI5 with >200 nm average grain size. A phase transition from rhombohedral to cubic structure is investigated via temperature-dependent X-ray diffraction (TD-XRD). Planar-junction photovoltaic (PV) devices are prepared based on the coevaporated rhombohedral AgBiI4 films, with titanium dioxide (TiO2) and poly(3-hexylthiophene) (P3HT) as electron- and hole-transport layers, respectively. The best-performing device exhibited a power conversion efficiency (PCE) of as high as 0.9% with open-circuit voltage (VOC) > 0.8 V in the reverse scan direction (with significant hysteresis).

Hybrid organic–inorganic lead halide perovskites have attracted broad interest because of their unique optical and electronic properties, as well as good processability. Thermal properties of these materials, often overlooked, can provide additional critical information for developing new methods of thin film preparation using, for example, melt processing—i.e., making films of hybrid perovskites by solidification of a thin layer of the melt liquid. We demonstrate that it is possible to tune the melting temperature of layered hybrid lead iodide perovskites over the range of more than 100 degrees by modifying the structures of alkylammonium-derived organic cations. Through the introduction of alkyl chain branching and extending the length of the base alkylammonium cation, melting temperatures of as low as 172 °C can be achieved and high quality thin films of layered hybrid lead iodide perovskites can be made using a solvent-free melt process with no additives and in ambient air. Additionally, we show that a similar concept can be translated to the corresponding layered bromides, with slightly higher observed melting temperatures. The design rules established here can guide the discovery of new melt-processable perovskite materials for low-cost high performance devices.

Perovskite solar cells have received substantial attention due to their potential for low-cost photovoltaic devices on flexible or rigid substrates. Thiocyanate (SCN)-containing additives, such as MASCN (MA = methylammonium), have been shown to control perovskite film crystallization and the film microstructure to achieve effective room-temperature perovskite absorber processing. Nevertheless, the crystallization pathways and mechanisms of perovskite formation involved in MASCN additive processing are far from clear. Using in situ X-ray diffraction and photoluminescence, we investigate the crystallization pathways of MAPbI3 and reveal the mechanisms of additive-assisted perovskite formation during spin coating and subsequent N2 drying. We confirm that MASCN induces large precursor aggregates in solution and, during spin coating, promotes the formation of the perovskite phase with lower nucleation density and overall larger initial nuclei size, which forms upon reaching supersaturation in solution, in addition to intermediate solvent-complex phases. Finally, during the subsequent N2 drying, MASCN facilitates the dissociation of these precursor aggregates and the solvate phases, leading to further growth of the perovskite crystals. Our results show that the nature of the intermediate phases and their formation/dissociation kinetics determine the nucleation and growth of the perovskite phase, which subsequently impact the film microstructure. These findings provide mechanistic insights underlying room-temperature, additive-assisted perovskite processing and help guide further development of such facile room-temperature synthesis routes.

Emerging photovoltaics (PVs), focuses on a variety of applications complementing large scale electricity generation. For instance, organic, dye-sensitized and some perovskite solar cells are considered in building integration, greenhouses, wearable and indoors, thereby motivating research on flexible, transparent, semitransparent, and multi-junction PVs. Nevertheless, it can be very time consuming to find or develop an up-to-date overview over the state-of-the-art performance for these systems and applications. Two important resources for record research cells efficiencies are the National Renewable Energy Laboratory chart and the efficiency tables compiled biannually by Martin Green and colleagues. Both publications provide an effective coverage over the established technologies, bridging research and industry. An alternative approach is proposed here summarizing the best reports in the diverse research subjects for emerging PVs. Best performance parameters are provided as a function of the photovoltaic bandgap energy for each technology and application, and are put into perspective using, e.g., the Shockley-Queisser limit. In all cases, the reported data correspond to published and/or properly described certified results, with enough details provided for prospective data reproduction. Additionally, the stability test energy yield (STEY) is included as an analysis parameter among state-of-the-art emerging PVs.

Emerging photovoltaics (PVs) focus on a variety of applications complementing large scale electricity generation. Organic, dye-sensitized, and some perovskite solar cells are considered in building integration, greenhouses, wearable, and indoor applications, thereby motivating research on flexible, transparent, semitransparent, and multi-junction PVs. Nevertheless, it can be very time consuming to find or develop an up-to-date overview of the state-of-the-art performance for these systems and applications. Two important resources for recording research cells efficiencies are the National Renewable Energy Laboratory chart and the efficiency tables compiled biannually by Martin Green and colleagues. Both publications provide an effective coverage over the established technologies, bridging research and industry. An alternative approach is proposed here summarizing the best reports in the diverse research subjects for emerging PVs. Best performance parameters are provided as a function of the photovoltaic bandgap energy for each technology and application, and are put into perspective using, e.g., the Shockley-Queisser limit. in all cases, the reported data correspond to published and/or properly described certified results, with enough details provided for prospective data reproduction. Additionally, the stability test energy yield is included as an analysis parameter among state-of-the-art emerging PVs., VDI/VD Innovation + Technik GmbH; SAOT - German Research Foundation (DFG)German Research Foundation (DFG); DFGGerman Research Foundation (DFG)European Commission [INST 90/917-1 FUGG, 182849149, SFB 953]; Energy Conversion Systems-from Materials to Devices [IGK 2495]; grant "ELF-PV-Design and development of solution processed functional materials for the next generations of PV technologies" [44-6521a/20/4]; grant "Solar Factory of the Future" [FKZ 20.2-3410.5-4-5]; SolTech Initiative by the Bavarian State Government; FAPESPFundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2017/11986-5]; ShellRoyal Dutch Shell; ANP (Brazil's National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation; National Science FoundationNational Science Foundation (NSF) [CBET-1702591]; US Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies OfficeUnited States Department of Energy (DOE) [34351]; European Research Council under the European Union's Horizon 2020 research and innovation program [742708]; Projekt DEAL, O.A. acknowledges the financial support from the VDI/VD Innovation + Technik GmbH (Project-title: PV-ZUM) and the SAOT funded by the German Research Foundation (DFG) in the framework of the German excellence initiative. C.J.B. acknowledges funding from DFG within INST 90/917-1 FUGG, the SFB 953 (DFG, project no. 182849149) and the IGK 2495 (Energy Conversion Systems-from Materials to Devices). C.J.B. further acknowledges the grants "ELF-PV-Design and development of solution processed functional materials for the next generations of PV technologies" (No. 44-6521a/20/4) and "Solar Factory of the Future" (FKZ 20.2-3410.5-4-5) and the SolTech Initiative by the Bavarian State Government. A.F.N. acknowledges support from FAPESP (Grant 2017/11986-5), Shell and the strategic importance of the support given by ANP (Brazil's National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation. R.R.L. gratefully acknowledges support from the National Science Foundation under grant CBET-1702591. N.K. acknowledges funding by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office, Agreement Number 34351. J.N. thanks the European Research Council for support under the European Union's Horizon 2020 research and innovation program (grant agreement No 742708).; Open access funding enabled and organized by Projekt DEAL.

To experimentally identify the character of radiative transitions in trigonal Cu2BaSnS4, we conduct temperature and excitation intensity dependent photoluminescence (PL) measurements in the temperature range of 15–300 K. The low-temperature near band edge PL spectrum is interpreted as the free exciton at 2.11 eV and the bound exciton at 2.08 eV, coupled with associated phonon-assisted transitions. In the low energy region, we assign the dominant defect emission at 1.96 eV to donor–acceptor-pair recombination and the weak broad emission at 1.6 eV to the free-to-bound transition. The activation energies and temperature shift for the radiative transitions are determined and discussed. Above 90 K, the free exciton recombination becomes the dominant radiative transition, with its energy shift mainly governed by the contribution of optical phonons.

Translation of chirality and asymmetry across structural motifs and length scales plays a fundamental role in nature, enabling unique functionalities in contexts ranging from biological systems to synthetic materials. Here, we introduce a structural chirality transfer across the organic–inorganic interface in two-dimensional hybrid perovskites using appropriate chiral organic cations. The preferred molecular configuration of the chiral spacer cations, R-(+)- or S-(−)-1-(1-naphthyl)ethylammonium and their asymmetric hydrogen-bonding interactions with lead bromide-based layers cause symmetry-breaking helical distortions in the inorganic layers, otherwise absent when employing a racemic mixture of organic spacers. First-principles modeling predicts a substantial bulk Rashba-Dresselhaus spin-splitting in the inorganic-derived conduction band with opposite spin textures between R- and S-hybrids due to the broken inversion symmetry and strong spin-orbit coupling. The ability to break symmetry using chirality transfer from one structural unit to another provides a synthetic design paradigm for emergent properties, including Rashba-Dresselhaus spin-polarization for hybrid perovskite spintronics and related applications., Inversion asymmetry imparts rich condensed matter phenomena in inorganic systems, and transmission of chirality across structural motifs is an attractive design strategy to break symmetry. Here, the authors use chiral organic cations to transfer structural chirality to inorganic layers in hybrid perovskites.

Crystalline metal halide perovskites (MHPs) have provided unprecedented advances in interdisciplinary fields of materials, electronics, and photonics. While crystallinity offers numerous advantages, the ability to access a glassy state with distinct properties provides unique opportunities to extend the associated structure-property relationship, as well as broaden the application space for MHPs. Amorphous analogs for MHPs have so far been restricted to high pressures, limiting detailed studies and applications. Here, a 2D MHP is structurally tailored using bulky chiral organic cations to exhibit an unusual confluence of exceptionally low melting temperature (175 °C) and inhibited crystallization. The chiral MHP can thus be melt-quenched into a stable glassy state, otherwise inhibited in the analogous racemic MHP. Facile and reversible switching between glassy and crystalline states is demonstrated for the chiral MHP, each with distinct optoelectronic character, opening new opportunities for applications including, for example nonvolatile memory, optical communication, and neuromorphic computing.