Improved charge extraction in inverted perovskite solar cells with dual-site-binding ligands.

Inverted (pin) perovskite solar cells (PSCs) afford improved operating stability in comparison to their nip counterparts but have lagged in power conversion efficiency (PCE). The energetic losses responsible for this PCE deficit in pin PSCs occur primarily at the interfaces between the perovskite and the charge-transport layers. Additive and surface treatments that use passivating ligands usually bind to a single active binding site: This dense packing of electrically resistive passivants perpendicular to the surface may limit the fill factor in pin PSCs. We identified ligands that bind two neighboring lead(II) ion (Pb2+) defect sites in a planar ligand orientation on the perovskite. We fabricated pin PSCs and report a certified quasi-steady state PCE of 26.15 and 24.74% for 0.05- and 1.04-square centimeter illuminated areas, respectively. The devices retain 95% of their initial PCE after 1200 hours of continuous 1 sun maximum power point operation at 65°C.

High-Efficiency Circularly Polarized Light-Emitting Diodes Based on Chiral Metal Nanoclusters.

Circularly polarized light-emitting diodes (CP-LEDs) are critical for next-generation optical technologies, ranging from holography to quantum information processing. Currently deployed chiral luminescent materials, with their intricate synthesis and processing and limited efficiency, are the main bottleneck for CP-LEDs. Chiral metal nanoclusters (MNCs) are potential CP-LED materials, given their ease of synthesis and processability as well as diverse structures and excited states. However, their films are usually plagued by inferior electronic quality and aggregation-caused photoluminescence quenching, necessitating their incorporation into host materials; without such a scheme, MNC-based LEDs exhibit external quantum efficiencies (EQEs) < 10%. Herein, we achieve an efficiency leap for both CP-LEDs and cluster-based LEDs by using novel chiral MNCs with aggregation-induced emission enhancement. CP-LEDs using enantiopure MNC films attain EQEs of up to 23.5%. Furthermore, by incorporating host materials, the devices yield record EQEs of up to 36.5% for both CP-LEDs and cluster-based LEDs, along with electroluminescence dissymmetry factors (|gEL|) of around 1.0 × 10-3. These findings open a new avenue for advancing chiral light sources for next-generation optoelectronics.

Homogeneous crystallization and buried interface passivation for perovskite tandem solar modules.

Scalable fabrication of all-perovskite tandem solar cells is challenging because the narrow-bandgap subcells made of mixed lead-tin (Pb-Sn) perovskite films suffer from nonuniform crystallization and inferior buried perovskite interfaces. We used a dopant from Good's list of biochemical buffers, aminoacetamide hydrochloride, to homogenize perovskite crystallization and used it to extend the processing window for blade-coating Pb-Sn perovskite films and to selectively passivate defects at the buried perovskite interface. The resulting all-perovskite tandem solar module exhibited a certified power conversion efficiency of 24.5% with an aperture area of 20.25 square centimeters.

Asymmetric Π-Bridge Engineering Enables High-Permittivity Benzo[1,2-B:4,5-b']Difuran-Conjugated Polymer for Efficient Organic Solar Cells.

Organic solar cells (OSCs) exhibit complex charge dynamics, which are closely correlated with the dielectric constant (ɛr ) of photovoltaic materials. In this work, a series of novel conjugated copolymers based on benzo[1,2-b:4,5-b']difuran (BDF) and benzotriazole (BTz) is designed and synthesized, which differ by the nature of π-bridge from one another. The PBDF-TF-BTz with asymmetric furan and thiophene π-bridge demonstrates a larger ɛr of 4.22 than PBDF-dT-BTz with symmetric thiophene π-bridge (3.15) and PBDF-dF-BTz with symmetric furan π-bridge (3.90). The PBDF-TF-BTz also offers more favorable molecular packing and appropriate miscibility with non-fullerene acceptor Y6 than its counterparts. The corresponding PBDF-TF-BTz:Y6 OSCs display efficient exciton dissociation, fast charge transport and collection, and reduced charge recombination, eventually leading to a power conversion efficiency of 17.01%. When introducing a fullerene derivative (PCBO-12) as a third component, the PBDF-TF-BTz:Y6:PCBO-12 OSCs yield a remarkable FF of 80.11% with a high efficiency of 18.10%, the highest value among all reported BDF-polymer-based OSCs. This work provides an effective approach to developing high-permittivity photovoltaic materials, showcasing PBDF-TF-BTz as a promising polymer donor for constructing high-performance OSCs.

2D Hybrid Perovskites Employing an Organic Cation Paired with a Neutral Molecule.

Two-dimensional (2D) hybrid perovskites harness the chemical and structural versatility of organic compounds. Here, we explore 2D perovskites that incorporate both a first organic component, a primary ammonium cation, and a second neutral organic module. Through the experimental examination of 42 organic pairs with a range of functional groups and organic backbones, we identify five crystallization scenarios that occur upon mixing. Only one leads to the cointercalation of the organic modules with distinct and extended interlayer spacing, which is observed with the aid of X-ray diffraction (XRD) pattern analysis combined with cross-sectional transmission electron microscopy (TEM) and elemental analysis. We present a picture in which complementary pairs, capable of forming intermolecular bonds, cocrystallize with multiple structural arrangements. These arrangements are a function of the ratio of organic content, annealing temperature, and substrate surface characteristics. We highlight how noncovalent bonds, particularly hydrogen and halogen bonding, enable the influence over the organic sublattice in hybrid halide perovskites.

Surface Engineering of Methylammonium Lead Bromide Perovskite Crystals for Enhanced X-ray Detection.

The surface quality of lead halide perovskite crystals can extremely influence their optoelectronic properties and device performance. Here, we report a surface engineering crystallization technique in which we in situ grow a polycrystalline methylammonium lead tribromide (MAPbBr3) film on top of bulk mm-sized single crystals. Such MAPbBr3 crystals with a MAPbBr3 passivating film display intense green emission under UV light. X-ray photoelectron spectroscopy demonstrates that these crystals with emissive surfaces are compositionally different from typical MAPbBr3 crystals that show no emission under UV light. Time-resolved photoluminescence and electrical measurements indicate that the MAPbBr3 film/MAPbBr3 crystals possess less surface defects compared to the bare MAPbBr3 crystals. Therefore, X-ray detectors fabricated using the surface-engineered MAPbBr3 crystals provide an almost 5 times improved sensitivity to X-rays and a more stable baseline drift with respect to the typical MAPbBr3 crystals.

Homomeric chains of intermolecular bonds scaffold octahedral germanium perovskites.

Perovskites with low ionic radii metal centres (for example, Ge perovskites) experience both geometrical constraints and a gain in electronic energy through distortion; for these reasons, synthetic attempts do not lead to octahedral [GeI6] perovskites, but rather, these crystallize into polar non-perovskite structures1-6. Here, inspired by the principles of supramolecular synthons7,8, we report the assembly of an organic scaffold within perovskite structures with the goal of influencing the geometric arrangement and electronic configuration of the crystal, resulting in the suppression of the lone pair expression of Ge and templating the symmetric octahedra. We find that, to produce extended homomeric non-covalent bonding, the organic motif needs to possess self-complementary properties implemented using distinct donor and acceptor sites. Compared with the non-perovskite structure, the resulting [GeI6]4- octahedra exhibit a direct bandgap with significant redshift (more than 0.5 eV, measured experimentally), 10 times lower octahedral distortion (inferred from measured single-crystal X-ray diffraction data) and 10 times higher electron and hole mobility (estimated by density functional theory). We show that the principle of this design is not limited to two-dimensional Ge perovskites; we implement it in the case of copper perovskite (also a low-radius metal centre), and we extend it to quasi-two-dimensional systems. We report photodiodes with Ge perovskites that outperform their non-octahedral and lead analogues. The construction of secondary sublattices that interlock with an inorganic framework within a crystal offers a new synthetic tool for templating hybrid lattices with controlled distortion and orbital arrangement, overcoming limitations in conventional perovskites.

High-Throughput Exploration of Triple-Cation Perovskites via All-in-One Compositionally-Graded Films.

Many devices heavily rely on combinatorial material optimization. However, new material alloys are classically developed by studying only a fraction of giant chemical space, while many intermediate compositions remain unmade in light of the lack of methods to synthesize gapless material libraries. Here report a high-throughput all-in-one material platform to obtain and study compositionally-tunable alloys from solution is reported. This strategy is applied to make all Csx MAy FAz PbI3 perovskite alloys (MA and FA stand for methylammonium and formamidinium, respectively), in less than 10 min, on a single film, on which 520 unique alloys are then studied. Through stability mapping of all these alloys in air supersaturated with moisture, a range of targeted perovskites are found, which are then chosen to make efficient and stable solar cells in relaxed fabrication conditions, in ambient air. This all-in-one platform provides access to an unprecedented library of compositional space with no unmade alloys, and hence aids in a comprehensive accelerated discovery of efficient energy materials.

Mixed Organic Cations Promote Ambient Light-Induced Formation of Metallic Lead in Lead Halide Perovskite Crystals.

One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam irradiation or thermal annealing. Here, we show that the quantity of metallic lead detected in perovskite crystals depends on the concentration and composition of the precursor solution. Through a controlled crystallization process, we grew black-colored mixed dimethylammonium (DMA)/methylammonium (MA) lead tribromide crystals. The black color is suggested to be due to the presence of small lead clusters. Despite the unexpected black coloring, the crystals show higher crystallinity and less defect density with respect to the standard yellow-colored DMA/MAPbBr3 crystals, as indicated by X-ray rocking curve and dark current measurements, respectively. While the formation of metallic lead could still be induced by external factors, the precursor solution composition and concentration can facilitate the formation of metallic lead during the crystallization process. Our results indicate that additional research is required to fully understand the perovskite precursor solution chemistry.

Ferroelectricity in Hybrid Perovskites.

Ferroelectric ceramics such as PbZrxTi1-xO3 (PZT) are widely applied in many fields, from medical to aerospace, because of their dielectric, piezoelectric, and pyroelectric properties. In the past few years, hybrid organic-inorganic halide perovskites have gradually attracted attention for their optical and electronic properties, including ferroelectricity, and for their low fabrication costs. In this Review, we first describe techniques that are used to quantify ferroelectric figures of merit of a material. We then discuss ferroelectricity in hybrid perovskites, starting from controversies in methylammonium iodoplumbate perovskites and then focusing on low-dimensional perovskites that offer an unambiguous platform to obtain ferroelectricity. Finally, we provide examples of the application of perovskite ferroelectrics in solar cells, LEDs, and X-ray detectors. We conclude that the vast structure-property tunability makes low-dimensional hybrid perovskites promising, but they have yet to offer ferroelectric figures of merit (e.g., saturated polarization) and thermal stability (e.g., Curie temperature) competitive with those of conventional oxide perovskite ferroelectric materials.

Oxidation-resistant all-perovskite tandem solar cells in substrate configuration.

The commonly-used superstrate configuration (depositing front subcell first and then depositing back subcell) in all-perovskite tandem solar cells is disadvantageous for long-term stability due to oxidizable narrow-bandgap perovskite assembled last and easily exposable to air. Here we reverse the processing order and demonstrate all-perovskite tandems in a substrate configuration (depositing back subcell first and then depositing front subcell) to bury oxidizable narrow-bandgap perovskite deep in the device stack. By using guanidinium tetrafluoroborate additive in wide-bandgap perovskite subcell, we achieve an efficiency of 25.3% for the substrate-configured all-perovskite tandem cells. The unencapsulated devices exhibit no performance degradation after storage in dry air for 1000 hours. The substrate configuration also widens the choice of flexible substrates: we achieve 24.1% and 20.3% efficient flexible all-perovskite tandem solar cells on copper-coated polyethylene naphthalene and copper metal foil, respectively. Substrate configuration offers a promising route to unleash the commercial potential of all-perovskite tandem solar cells.

NiOx for interface and work function engineering in carbon-based all-inorganic perovskite solar cells.

Carbon-based all-inorganic perovskite solar cells (C-IPSCs) are stable, upscalable and have low CO2-footprint to fabricate. However, they are inefficient in converting light to electricity due to poor hole extraction at perovskite/carbon interface. Here we enable an efficient hole extraction in C-IPSCs with the aid of inorganic p-type nickel oxide nanoparticles (NiOx-NPs) at the interface and in carbon. By tailoring the work function (WF) of carbon, and reducing the energy-level misalignment at the perovskite/carbon interface, NiOx-NPs enable efficient hole transfer, reduce charge recombination and minimize energy loss. As a result, we report 15.01% and 11.02% efficiencies for CsPbI2Br and CsPbIBr2 C-IPSCs, respectively, with a high open-circuit voltage of ∼1.3 V. Unencapsulated interface-modified CsPbI2Br devices maintained 92.8% of their initial efficiency at ambient conditions after nearly 2,000 h; and 94.6% after heating at 60 °C for 170 h. This strategy to tailor carbon interface with perovskite offers an important knob in improving C-IPSCs performance.

A Roadmap for Efficient and Stable All-Perovskite Tandem Solar Cells from a Chemistry Perspective.

Multijunction tandem solar cells offer a promising route to surpass the efficiency limit of single-junction solar cells. All-perovskite tandem solar cells are particularly attractive due to their high power conversion efficiency, now reaching 28% despite being made with relatively easy fabrication methods. In this review, we summarize the progress in all-perovskite tandem solar cells. We then discuss the scientific and engineering challenges associated with both absorbers and functional layers and offer strategies for improving the efficiency and stability of all-perovskite tandem solar cells from the perspective of chemistry.

Single-Crystal Perovskite Solar Cells Exhibit Close to Half A Millimeter Electron-Diffusion Length.

Single-crystal halide perovskites exhibit photogenerated-carriers of high mobility and long lifetime, making them excellent candidates for applications demanding thick semiconductors, such as ionizing radiation detectors, nuclear batteries, and concentrated photovoltaics. However, charge collection depreciates with increasing thickness; therefore, tens to hundreds of volts of external bias is required to extract charges from a thick perovskite layer, leading to a considerable amount of dark current and fast degradation of perovskite absorbers. However, extending the carrier-diffusion length can mitigate many of the anticipated issues preventing the practical utilization of perovskites in the abovementioned applications. Here, single-crystal perovskite solar cells that are up to 400 times thicker than state-of-the-art perovskite polycrystalline films are fabricated, yet retain high charge-collection efficiency in the absence of an external bias. Cells with thicknesses of 110, 214, and 290 µm display power conversion efficiencies (PCEs) of 20.0, 18.4, and 14.7%, respectively. The remarkable persistence of high PCEs, despite the increase in thickness, is a result of a long electron-diffusion length in those cells, which was estimated, from the thickness-dependent short-circuit current, to be ≈0.45 mm under 1 sun illumination. These results pave the way for adapting perovskite devices to optoelectronic applications in which a thick active layer is essential.

High-Throughput Synthesis of Thin Films for the Discovery of Energy Materials: A Perspective.

Thin films are an integral part of many electronic and optoelectronic devices. They also provide an excellent platform for material characterization. Therefore, strategies for the fabrication of thin films are constantly developed and have significantly benefited from the advent of high-throughput synthesis (HTS) platforms. This perspective summarizes recent advances in HTS of thin films from experimentalists' point of view. The work analyzes general strategies of HTS and then discusses their use in developing new energy materials for applications that rely on thin films, such as solar cells, light-emitting diodes, batteries, superconductors, and thermoelectrics. The perspective also summarizes some key challenges and opportunities in the HTS of thin films.

Synergistic Effects of Bipolar Additives on Grain Boundary-Mediated Charge Transport for Efficient Carbon-Based Inorganic Perovskite Solar Cells.

Carbon-based all-inorganic CsPbIxBr3-x perovskite solar cells offer high stability against heat and humidity and a suitable band gap for tandem and semitransparent photovoltaics. In CsPbIxBr3-x perovskite films, the defects at grain boundaries (GBs) cause charge trapping, reducing the efficiency of the cell. Electronic deactivation of GB has been a conventional strategy to suppress the trapping, but at the cost of charge carrier transport through the boundaries. Here, we turn the GBs into benign charge transport pathways with the aid of bipolar charge transport semiconductors, namely, Ti3C2TX (MXene) and Spiro-OMeTAD, respectively. Thanks to the synergistic effects of both n- and p-type transport media, the charge transport is improved and balanced at the GBs. As a result, the cells achieve an efficiency of 12.7%, the highest among all low-temperature-processed carbon-based inorganic perovskite solar cells. Benign GBs also lead to enhanced light and aging stabilities. Our work demonstrates a proof-of-concept strategy of benign electronic modulation of GBs for solution-processed perovskite solar cells.

Coupling Perovskite Quantum Dot Pairs in Solution using a Nanoplasmonic Assembly.

Perovskite quantum dots (PQDs) provide a robust solution-based approach to efficient solar cells, bright light emitting devices, and quantum sources of light. Quantifying heterogeneity and understanding coupling between dots is critical for these applications. We use double-nanohole optical trapping to size individual dots and correlate to emission energy shifts from quantum confinement. We were able to assemble a second dot in the trap, which allows us to observe the coupling between dots. We observe a systematic red-shift of 1.1 ± 0.6 meV in the emission wavelength. Theoretical analysis shows that the observed shift is consistent with resonant energy transfer and is unusually large due to moderate-to-large quantum confinement in PQDs. This demonstrates the promise of PQDs for entanglement in quantum information applications. This work enables future in situ control of PQD growth as well as studies of the coupling between small PQD assemblies with quantum information applications in mind.

Magnetic optical rotary dispersion and magnetic circular dichroism in methylammonium lead halide perovskites.

Large magnetic optical rotary dispersion (Faraday rotation) has been demonstrated recently in methylammonium lead bromide. Here, we investigate the prospect of extending the active spectral range by altering the halogen. We also investigate the origins of large Faraday rotation in these diamagnetic materials using magnetic circular dichroism (MCD) spectroscopy and the Kramers-Kronig relations. We find that, while MAPbCl3 (MA = methylammonium) single crystals exhibit a large Verdet constant in the blue, no appreciable Faraday rotation is observed in the red/near infra-red for MAPbI3 single crystals. However, in all film samples, we find clear evidence of large MCD resulting from the Zeeman splitting of the highly resonant 1s exciton state. Our Kramers-Kronig calculations of Faraday rotation based on MCD data matches well with the dispersion of our experimental data for MAPbCl3 and MAPbBr3 , with some deviation in magnitude-demonstrating the excitonic nature of Faraday rotation in these materials. However, our calculations predict significant Faraday rotation in MAPbI3 , contrary to our experimental results, indicating a potential discrepancy between the properties of the thin film and single crystal.

Quantum Dot Self-Assembly Enables Low-Threshold Lasing.

Perovskite quantum dots (QDs) are of interest for solution-processed lasers; however, their short Auger lifetime has limited lasing operation principally to the femtosecond temporal regime the photoexcitation levels to achieve optical gain threshold are up to two orders of magnitude higher in the nanosecond regime than in the femtosecond. Here the authors report QD superlattices in which the gain medium facilitates excitonic delocalization to decrease Auger recombination and in which the macroscopic dimensions of the structures provide the optical feedback required for lasing. The authors develope a self-assembly strategy that relies on sodiumd-an assembly director that passivates the surface of the QDs and induces self-assembly to form ordered three-dimensional cubic structures. A density functional theory model that accounts for the attraction forces between QDs allows to explain self-assembly and superlattice formation. Compared to conventional organic-ligand-passivated QDs, sodium enables higher attractive forces, ultimately leading to the formation of micron-length scale structures and the optical faceting required for feedback. Simultaneously, the decreased inter-dot distance enabled by the new ligand enhances exciton delocalization among QDs, as demonstrated by the dynamically red-shifted photoluminescence. These structures function as the lasing cavity and the gain medium, enabling nanosecond-sustained lasing with a threshold of 25 µJ cm-2 .

All-Inorganic Quantum-Dot LEDs Based on a Phase-Stabilized α-CsPbI3 Perovskite.

The all-inorganic nature of CsPbI3 perovskites allows to enhance stability in perovskite devices. Research efforts have led to improved stability of the black phase in CsPbI3 films; however, these strategies-including strain and doping-are based on organic-ligand-capped perovskites, which prevent perovskites from forming the close-packed quantum dot (QD) solids necessary to achieve high charge and thermal transport. We developed an inorganic ligand exchange that leads to CsPbI3 QD films with superior phase stability and increased thermal transport. The atomic-ligand-exchanged QD films, once mechanically coupled, exhibit improved phase stability, and we link this to distributing strain across the film. Operando measurements of the temperature of the LEDs indicate that KI-exchanged QD films exhibit increased thermal transport compared to controls that rely on organic ligands. The LEDs exhibit a maximum EQE of 23 % with an electroluminescence emission centered at 640 nm (FWHM: ≈31 nm). These red LEDs provide an operating half-lifetime of 10 h (luminance of 200 cd m-2 ) and an operating stability that is 6× higher than that of control devices.