Cation exchange synthesis of AgBiS2 quantum dots for highly efficient solar cells.

Silver bismuth sulfide (AgBiS2) nanocrystals have emerged as a promising eco-friendly, low-cost solar cell absorber material. Their direct synthesis often relies on the hot-injection method, requiring the application of high temperatures and vacuum for prolonged times. Here, we demonstrate an alternative synthetic approach via a cation exchange reaction. In the first-step, bis(stearoyl)sulfide is used as an air-stable sulfur precursor for the synthesis of small, monodisperse Ag2S nanocrystals at room-temperature. In a second step, bismuth cations are incorporated into the nanocrystal lattice to form ternary AgBiS2 nanocrystals, without altering their size and shape. When implemented into photovoltaic devices, AgBiS2 nanocrystals obtained by cation exchange reach power conversion efficiencies of up to 7.35%, demonstrating the efficacy of the new synthetic approach for the formation of high-quality, ternary semiconducting nanocrystals.

Halide Segregated Crystallization of Mixed-Halide Perovskites Revealed by In Situ GIWAXS.

Mixed-halide perovskites of the composition MAPb(BrxI1-x)3, which seem to exhibit a random and uniform distribution of halide ions in the absence of light, segregate into bromide- and iodide-rich phases under illumination. This phenomenon of halide segregation has been widely investigated in the photovoltaics context since it is detrimental for the material properties and ultimately the device performance of these otherwise very attractive materials. A full understanding of the mechanisms and driving forces has remained elusive. In this work, a study of the crystallization pathways and the mixing behavior during deposition of MAPb(BrxI1-x)3 thin films with varying halide ratios is presented. In situ grazing incidence wide-angle scattering (GIWAXS) reveals the distinct crystallization behavior of mixed-halide perovskite compositions during two different fabrication routes: nitrogen gas-quenching and the lead acetate route. The perovskite phase formation of mixed-halide thin films hints toward a segregation tendency since separate crystallization pathways are observed for iodide- and bromide-rich phases within the mixed compositions. Crystallization of the bromide perovskite phase (MAPbBr3) is already observed during spin coating, while the iodide-based fraction of the composition forms solvent complexes as an intermediate phase, only converting into the perovskite phase upon thermal annealing. These parallel crystallization pathways result in mixed-halide perovskites forming from initially halide-segregated phases only under the influence of heating.

Solvent-antisolvent interactions in metal halide perovskites.

The fabrication of metal halide perovskite films using the solvent-engineering method is increasingly common. In this method, the crystallisation of the perovskite layer is triggered by the application of an antisolvent during the spin-coating of a perovskite precursor solution. Herein, we introduce the current state of understanding of the processes involved in the crystallisation of perovskite layers formed by solvent engineering, focusing in particular on the role of antisolvent properties and solvent-antisolvent interactions. By considering the impact of the Hansen solubility parameters, we propose guidelines for selecting the appropriate antisolvent and outline open questions and future research directions for the fabrication of perovskite films by this method.

Elucidating Structure Formation in Highly Oriented Triple Cation Perovskite Films.

Metal halide perovskites are an emerging class of crystalline semiconductors of great interest for application in optoelectronics. Their properties are dictated not only by their composition, but also by their crystalline structure and microstructure. While significant efforts are dedicated to the development of strategies for microstructural control, significantly less is known about the processes that govern the formation of their crystalline structure in thin films, in particular in the context of crystalline orientation. This work investigates the formation of highly oriented triple cation perovskite films fabricated by utilizing a range of alcohols as an antisolvent. Examining the film formation by in situ grazing-incidence wide-angle X-ray scattering reveals the presence of a short-lived highly oriented crystalline intermediate, which is identified as FAI-PbI2 -xDMSO. The intermediate phase templates the crystallization of the perovskite layer, resulting in highly oriented perovskite layers. The formation of this dimethylsulfoxide (DMSO) containing intermediate is triggered by the selective removal of N,N-dimethylformamide (DMF) when alcohols are used as an antisolvent, consequently leading to differing degrees of orientation depending on the antisolvent properties. Finally, this work demonstrates that photovoltaic devices fabricated from the highly oriented films, are superior to those with a random polycrystalline structure in terms of both performance and stability.

Oxygen-induced degradation in AgBiS2 nanocrystal solar cells.

AgBiS2 nanocrystal solar cells are among the most sustainable emerging photovoltaic technologies. Their environmentally-friendly composition and low energy consumption during fabrication make them particularly attractive for future applications. However, much remains unknown about the stability of these devices, in particular under operational conditions. In this study, we explore the effects of oxygen and light on the stability of AgBiS2 nanocrystal solar cells and identify its dependence on the charge extraction layers. Normally, the rate of oxygen-induced degradation of nanocrystals is related to their ligands, which determine the access sites by steric hindrance. We demonstrate that the ligands, commonly used in AgBiS2 solar cells, also play a crucial chemical role in the oxidation process. Specifically, we show that the tetramethylammonium iodide ligands enable their oxidation, leading to the formation of bismuth oxide and silver sulphide. Additionally, the rate of oxidation is impacted by the presence of water, often present at the surface of the ZnO electron extraction layer. Moreover, the degradation of the organic hole extraction layer also impacts the overall device stability and the materials' photophysics. The understanding of these degradation processes is necessary for the development of mitigation strategies for future generations of more stable AgBiS2 nanocrystal solar cells.

23.7% Efficient inverted perovskite solar cells by dual interfacial modification.

Despite remarkable progress, the performance of lead halide perovskite solar cells fabricated in an inverted structure lags behind that of standard architecture devices. Here, we report on a dual interfacial modification approach based on the incorporation of large organic cations at both the bottom and top interfaces of the perovskite active layer. Together, this leads to a simultaneous improvement in both the open-circuit voltage and fill factor of the devices, reaching maximum values of 1.184 V and 85%, respectively, resulting in a champion device efficiency of 23.7%. This dual interfacial modification is fully compatible with a bulk modification of the perovskite active layer by ionic liquids, leading to both efficient and stable inverted architecture devices.

A general approach to high-efficiency perovskite solar cells by any antisolvent.

Deposition of perovskite films by antisolvent engineering is a highly common method employed in perovskite photovoltaics research. Herein, we report on a general method that allows for the fabrication of highly efficient perovskite solar cells by any antisolvent via manipulation of the antisolvent application rate. Through detailed structural, compositional, and microstructural characterization of perovskite layers fabricated by 14 different antisolvents, we identify two key factors that influence the quality of the perovskite layer: the solubility of the organic precursors in the antisolvent and its miscibility with the host solvent(s) of the perovskite precursor solution, which combine to produce rate-dependent behavior during the antisolvent application step. Leveraging this, we produce devices with power conversion efficiencies (PCEs) that exceed 21% using a wide range of antisolvents. Moreover, we demonstrate that employing the optimal antisolvent application procedure allows for highly efficient solar cells to be fabricated from a broad range of precursor stoichiometries.

Ruddlesden-Popper-Phase Hybrid Halide Perovskite/Small-Molecule Organic Blend Memory Transistors.

Controlling the morphology of metal halide perovskite layers during processing is critical for the manufacturing of optoelectronics. Here, a strategy to control the microstructure of solution-processed layered Ruddlesden-Popper-phase perovskite films based on phenethylammonium lead bromide ((PEA)2 PbBr4 ) is reported. The method relies on the addition of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C8 -BTBT) into the perovskite formulation, where it facilitates the formation of large, near-single-crystalline-quality platelet-like (PEA)2 PbBr4 domains overlaid by a ≈5-nm-thin C8 -BTBT layer. Transistors with (PEA)2 PbBr4 /C8 -BTBT channels exhibit an unexpectedly large hysteresis window between forward and return bias sweeps. Material and device analysis combined with theoretical calculations suggest that the C8 -BTBT-rich phase acts as the hole-transporting channel, while the quantum wells in (PEA)2 PbBr4 act as the charge storage element where carriers from the channel are injected, stored, or extracted via tunneling. When tested as a non-volatile memory, the devices exhibit a record memory window (>180 V), a high erase/write channel current ratio (104 ), good data retention, and high endurance (>104 cycles). The results here highlight a new memory device concept for application in large-area electronics, while the growth technique can potentially be exploited for the development of other optoelectronic devices including solar cells, photodetectors, and light-emitting diodes.

Effect of Precursor Stoichiometry on the Performance and Stability of MAPbBr3 Photovoltaic Devices.

The wide-bandgap methylammonium lead bromide perovskite is promising for applications in tandem solar cells and light-emitting diodes. Despite its utility, there is a limited understanding of its reproducibility and stability. Herein, the dependence of the properties, performance, and shelf storage of thin films and devices on minute changes to the precursor solution stoichiometry is examined in detail. Although photovoltaic cells based on these solution changes exhibit similar initial performance, shelf storage depends strongly on precursor solution stoichiometry. While all devices exhibit some degree of healing, bromide-deficient films show a remarkable improvement, more than doubling in their photoconversion efficiency. Photoluminescence spectroscopy experiments performed under different atmospheres suggest that this increase is due, in part, to a trap-healing mechanism that occurs upon exposure to the environment. The results highlight the importance of understanding and manipulating defects in lead halide perovskites to produce long-lasting, stable devices.

Vacuum-Induced Degradation of 2D Perovskites.

Two-dimensional (2D) hybrid organic-inorganic perovskites have recently attracted the attention of the scientific community due to their exciting optical and electronic properties as well as enhanced stability upon exposure to environmental factors. In this work, we investigate 2D perovskite layers with a range of organic cations and report on the Achilles heel of these materials-their significant degradation upon exposure to vacuum. We demonstrate that vacuum exposure induces the formation of a metallic lead species, accompanied by a loss of the organic cation from the perovskite. We investigate the dynamics of this reaction, as well as the influence of other factors, such as X-ray irradiation. Furthermore, we characterize the effect of degradation on the microstructure of the 2D layers. Our study highlights that despite earlier reports, 2D perovskites may exhibit instabilities, the chemistry of which should be identified and investigated in order to develop suitable mitigation strategies.

Efficient and Stable PbS Quantum Dot Solar Cells by Triple-Cation Perovskite Passivation.

Solution-processed quantum dots (QDs) have a high potential for fabricating low-cost, flexible, and large-scale solar energy harvesting devices. It has recently been demonstrated that hybrid devices employing a single monovalent cation perovskite solution for PbS QD surface passivation exhibit enhanced photovoltaic performance when compared to standard ligand passivation. Herein, we demonstrate that the use of a triple cation Cs0.05(MA0.17FA0.83)0.95Pb(I0.9Br0.1)3 perovskite composition for surface passivation of the quantum dots results in highly efficient solar cells, which maintain 96% of their initial performance after 1200 h shelf storage. We confirm perovskite shell formation around the PbS nanocrystals by a range of spectroscopic techniques as well as high-resolution transmission electron microscopy. We find that the triple cation shell results in a favorable energetic alignment to the core of the dot, resulting in reduced recombination due to charge confinement without limiting transport in the active layer. Consequently, photovoltaic devices fabricated via a single-step film deposition reached a maximum AM1.5G power conversion efficiency of 11.3% surpassing most previous reports of PbS solar cells employing perovskite passivation.

Enhancing the Open-Circuit Voltage of Perovskite Solar Cells by Embedding Molecular Dipoles within Their Hole-Blocking Layer.

Engineering the energetics of perovskite photovoltaic devices through deliberate introduction of dipoles to control the built-in potential of the devices offers an opportunity to enhance their performance without the need to modify the active layer itself. In this work, we demonstrate how the incorporation of molecular dipoles into the bathocuproine (BCP) hole-blocking layer of inverted perovskite solar cells improves the device open-circuit voltage (VOC) and, consequently, their performance. We explore a series of four thiaazulenic derivatives that exhibit increasing dipole moments and demonstrate that these molecules can be introduced into the solution-processed BCP layer to effectively increase the built-in potential within the device without altering any of the other device layers. As a result, the VOC of the devices is enhanced by up to 130 mV, with larger dipoles resulting in higher VOC. To investigate the limitations of this approach, we employ numerical device simulations that demonstrate that the highest dipole derivatives used in this work eliminate all limitations on the VOC stemming from the built-in potential of the device.

Tailoring Ultrafast Singlet Fission by the Chemical Modification of Phenazinothiadiazoles.

Quantum chemistry and time-resolved spectroscopy are applied to rationalize how singlet fission (SF) is affected by systematic chemical modifications introduced into phenazinothiadiazoles (PTD). Substitution of the terminal aromatic ring of TIPS-tetracene by a thiadiazole group leads to a considerable change in the relative energies of its S1 and T1 states. Thus, in contrast to TIPS-tetracene, SF becomes exothermic for various PTD derivatives, which show S1-2T1 energy differences as high as 0.15 eV. This enables SF in PTD as corroborated by femtosecond transient absorption spectroscopy and TD-DFT calculations. The latter report T-T spectra consistent with thin film UV-vis femtosecond transient absorption of PTDs at long delays. TD-DFT calculations also show that the S1-T1 energy gap can be rationally tuned by introducing N atoms into the aromatic scaffold and by the halogenation of one side ring of the PTD. In addition, the specific S1-to-1(T1T1) electronic coupling depends on the crystal morphology and the electronic properties simultaneously. Thus, both of them govern the strength and the interplay between direct and superexchange couplings, which in the most favorable cases accelerate SF to rate constants beyond (100 fs)-1. Remarkably, direct coupling was found to contribute considerably to the total effective coupling and even to dominate it for some PTDs investigated here. A quantum yield of 200% is obtained on the early picosecond time scale for all compounds studied here, which is reduced to 100% due to triplet-triplet annihilation after a few nanoseconds.

Gold-Catalyzed Facile Synthesis and Crystal Structures of Benzene-/Naphthalene-Based Bispentalenes as Organic Semiconductors.

The gold-catalyzed facile synthesis of U-shaped and S-shaped bispentalenes is described from easily available tetra(arylethynyl)-benzenes and -naphthalenes. The optoelectronic and transistor properties were also investigated. The selectivity between the U-shaped and S-shaped bispentalene isomers can be tuned by the bulkiness of the ligand and the substrates. The S-shaped naphthalene-based bispentalene shows a one-dimensional face-to-face packing pattern in solid state and a good hole mobility, indicating that the S-shaped bispentalene core is highly suitable for transistor applications. The gold-catalyzed annulation of tetraynes provides a useful protocol in the synthesis of bispentalenes for organic semiconductors.

Probing charge transfer states at organic and hybrid internal interfaces by photothermal deflection spectroscopy.

In organic and hybrid photovoltaic devices, the asymmetry required for charge separation necessitates the use of a donor and an acceptor material, resulting in the formation of internal interfaces in the device active layer. While the core objective of these interfaces is to facilitate charge separation, bound states between electrons and holes may form across them, resulting in a loss mechanism that diminishes the performance of the solar cells. These interfacial transitions appear in organic systems as charge transfer (CT) states and as bound charge pairs (BCP) in hybrid systems. Despite being similar, the latter are far less investigated. Herein, we employ photothermal deflection spectroscopy and pump-push-probe experiments in order to determine the characteristics and dynamics of interfacial states in two model systems: an organic P3HT:PCBM and hybrid P3HT:ZnO photovoltaic layer. By controlling the area of the internal interface, we identify CT states between 1.4 eV and 1.8 eV in the organic bulk-heterojunction (BHJ) and BCP between 1.1 eV and 1.4 eV in the hybrid BHJ. The energetic distribution of these states suggests that they not only contribute to losses in photocurrent, but also significantly limit the possible maximum open circuit voltage obtainable from these devices.

Effect of Crystal Grain Orientation on the Rate of Ionic Transport in Perovskite Polycrystalline Thin Films.

In this work, we examine the effect of microstructure on ion-migration-induced photoluminescence (PL) quenching in methylammonium lead iodide perovskite films. Thin films were fabricated by two methods: spin-coating, which results in randomly oriented perovskite grains, and zone-casting, which results in aligned grains. As an external bias is applied to these films, migration of ions causes a quenching of the PL signal in the vicinity of the anode. The evolution of this PL-quenched zone is less uniform in the spin-coated devices than in the zone-cast ones, suggesting that the relative orientation of the crystal grains plays a significant role in the migration of ions within polycrystalline perovskite. We simulate this effect via a simple Ising model of ionic motion across grains in the perovskite thin film. The results of this simulation align closely with the observed experimental results, further solidifying the correlation between crystal grain orientation and the rate of ionic transport.

Iodine Migration and its Effect on Hysteresis in Perovskite Solar Cells.

The migration and accumulation of iodide ions create a modulation of the respective interfacial barriers causing the hysteresis in solar cells based on methylammonium lead iodide perovskites. Iodide ions are identified as the migrating species by measuring temperature dependent current-transients and photoelectron spectroscopy. The involved changes in the built-in potential due to ion migration are directly measured by electroabsorption spectroscopy.

Halogenated Symmetrical Tetraazapentacenes: Synthesis, Structures, and Properties.

We herein describe the synthesis and property evaluation of several brominated and chlorinated tetraazapentacenes. The targets were obtained by thermal condensation of 2,5-dihydroxyquinone with 4,5-dichloro-, 2,6-dichloro-, and 4,5-dibromo-1,2-phenylenediamine, followed by oxidation with hot acidic dichromate. Double alkynylation, reductive deoxygenation, and subsequent oxidation using MnO2 furnishes the target compounds. Absorption spectra, electrochemistry, and single crystal structures of the targets are reported. The 1,4,8,11-tetrachlorotetraazapentacene (1,4,8,11-tetrachloroquinoxalino[2,3-b]phenazine) carrying its chlorine atoms in the peri-positions packs in a herringbone type arrangement, while the isomer (2,3,9,10-tetrachloroquinoxalino[2,3-b]phenazine, with the chlorine atoms in the east and west positions) packs in one-dimensional stacks. In all cases, the reduction potentials and the calculated LUMO-positions are decreased by the introduction of the halogen atoms.

Coronene-Containing N-Heteroarenes: 13 Rings in a Row.

We describe the modular synthesis of three novel large N-heteroarenes, containing 9, 11, and 13 annulated rings. This modular system features fused azaacene units to a coronene nucleus. We evaluate the optical and electronic properties and the solid-state packing of the targets. The electronic properties of the 13-ring N-heteroarene allow the fabrication of a proof-of-concept thin-film transistor. Electron mobilities up to 8 × 10(-4) cm/(V s) were obtained for polycrystalline films.

Reverse Engineering of Conjugated Microporous Polymers: Defect Structures of Tetrakis(4-ethynylphenyl)stannane Networks.

Two different conjugated microporous polymers (CMPs) based on tetrakis(4-ethynylphenyl)stannane as the repeating unit were synthesized and their BET surfaces and thermal properties were investigated. The first direct method to elucidate the molecular structure of the organic linkers between the tin centers by digestion of the CMP is described. Selective cleavage of the tin-carbon bonds with chloroacetic acid afforded the isolated bridging units and provided insight into the surprisingly varied chemical composition of these networks.