Synchrotron Radiation-Based In Situ GIWAXS for Metal Halide Perovskite Solution Spin-Coating Fabrication.

Solution-processable perovskite-based devices are potentially very interesting because of their relatively cheap fabrication cost but outstanding optoelectronic performance. However, the solution spin-coating process involves complicated processes, including perovskite solution droplets, nucleation of perovskite, and formation of intermediate perovskite films, resulting in complicated crystallization pathways for perovskite films under annealing. Understanding and therefore controlling the fabrication process of perovskites is difficult. Recently, synchrotron radiation-based in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) techniques, which possess the advantages of high collimation, high resolution, and high brightness, have enabled to bridge complicated perovskite structure information with device performance by revealing the real-time crystallization pathways of perovskites during the spin-coating process. Herein, the developments of synchrotron radiation-based in situ GIWAXS are discussed in the study of the crystallization process of perovskites, especially revealing the important crystallization mechanisms of state-of-the-art perovskite optoelectronic devices with high performance. At the end, several potential applications and challenges associated with in situ GIWAXS techniques for perovskite-based devices are highlighted.

Photovoltaic nanocells for high-performance large-scale-integrated organic phototransistors.

A high-performance large-scale-integrated organic phototransistor needs a semiconductor layer that maintains its photoelectric conversion ability well during high-resolution pixelization. However, lacking a precise design for the nanoscale structure, a trade-off between photoelectric performance and device miniaturization greatly limits the success in commercial application. Here we demonstrate a photovoltaic-nanocell enhancement strategy, which overcomes the trade-off and enables high-performance organic phototransistors at a level beyond large-scale integration. Embedding a core-shell photovoltaic nanocell based on perovskite quantum dots in a photocrosslinkable organic semiconductor, ultralarge-scale-integrated (>221 units) imaging chips are manufactured using photolithography. 27 million pixels are interconnected and the pixel density is 3.1 × 106 units cm-2, at least two orders of magnitude higher than in existing organic imaging chips and equivalent to the latest commercial full-frame complementary metal-oxide-semiconductor camera chips. The embedded photovoltaic nanocells induce an in situ photogating modulation and enable photoresponsivity and detectivity of 6.8 × 106 A W-1 and 1.1 × 1013 Jones (at 1 Hz), respectively, achieving the highest values of organic imaging chips at large-scale or higher integration. In addition, a very-large-scale-integrated (>216 units) stretchable biomimetic retina based on photovoltaic nanocells is manufactured for neuromorphic imaging recognition with not only resolution but also photoresponsivity and power consumption approaching those of the biological counterpart.

Fabrication of red-emitting perovskite LEDs by stabilizing their octahedral structure.

Light-emitting diodes (LEDs) based on metal halide perovskites (PeLEDs) with high colour quality and facile solution processing are promising candidates for full-colour and high-definition displays1-4. Despite the great success achieved in green PeLEDs with lead bromide perovskites5, it is still challenging to realize pure-red (620-650 nm) LEDs using iodine-based counterparts, as they are constrained by the low intrinsic bandgap6. Here we report efficient and colour-stable PeLEDs across the entire pure-red region, with a peak external quantum efficiency reaching 28.7% at 638 nm, enabled by incorporating a double-end anchored ligand molecule into pure-iodine perovskites. We demonstrate that a key function of the organic intercalating cation is to stabilize the lead iodine octahedron through coordination with exposed lead ions and enhanced hydrogen bonding with iodine. The molecule synergistically facilitates spectral modulation, promotes charge transfer between perovskite quantum wells and reduces iodine migration under electrical bias. We realize continuously tunable emission wavelengths for iodine-based perovskite films with suppressed energy loss due to the decrease in bond energy of lead iodine in ionic perovskites as the bandgap increases. Importantly, the resultant devices show outstanding spectral stability and a half-lifetime of more than 7,600 min at an initial luminance of 100 cd m-2.

Revealing the vertical structure of in-situ fabricated perovskite nanocrystals films toward efficient pure red light-emitting diodes.

The development of efficient perovskite light-emitting diodes (PeLEDs) relies strongly on the fabrication of perovskite films with rationally designed structures (grain size, composition, surface, etc.). Therefore, an understanding of structure-performance relationships is of vital importance for developing high-performance perovskite devices, particularly for devices with in-situ fabricated perovskite nanocrystal films. In this study, we reveal the vertical structure of an in-situ fabricated quasi-two-dimensional perovskite film. By combining time-of-flight secondary ion mass spectrometry, energy dispersive spectroscopy, grazing incidence wide-angle X-ray scattering (GIWAXS), and low-temperature photoluminescence spectra, we illustrate that the resulting in-situ fabricated DPPA2Csn-1Pbn(Br0.3I0.7)3n+1 (DPPA+: 3,3-diphenylpropylammonium) film has a gradient structure with a very thin layer of ligands on the surface, predominantly small-n domains at the top, and predominantly large-n domains at the bottom owing to the solubility difference of the precursors. In addition, GIWAXS measurements show that the domain of n = 2 on the top layer has an ordered in-plane alignment. Based on the understanding of the film structure, we developed an in-situ fabrication process with ligand exchange to achieve efficient pure red PeLEDs at 638 nm with an average external quantum efficiency (EQE) of 7.4%. The optimized device had a maximum luminance of 623 cd/m2 with a peak EQE of 9.7%.

Acceleration of radiative recombination for efficient perovskite LEDs.

The increasing demands for more efficient and brighter thin-film light-emitting diodes (LEDs) in flat-panel display and solid-state lighting applications have promoted research into three-dimensional (3D) perovskites. These materials exhibit high charge mobilities and low quantum efficiency droop1-6, making them promising candidates for achieving efficient LEDs with enhanced brightness. To improve the efficiency of LEDs, it is crucial to minimize nonradiative recombination while promoting radiative recombination. Various passivation strategies have been used to reduce defect densities in 3D perovskite films, approaching levels close to those of single crystals3. However, the slow radiative (bimolecular) recombination has limited the photoluminescence quantum efficiencies (PLQEs) of 3D perovskites to less than 80% (refs. 1,3), resulting in external quantum efficiencies (EQEs) of LED devices of less than 25%. Here we present a dual-additive crystallization method that enables the formation of highly efficient 3D perovskites, achieving an exceptional PLQE of 96%. This approach promotes the formation of tetragonal FAPbI3 perovskite, known for its high exciton binding energy, which effectively accelerates the radiative recombination. As a result, we achieve perovskite LEDs with a record peak EQE of 32.0%, with the efficiency remaining greater than 30.0% even at a high current density of 100 mA cm-2. These findings provide valuable insights for advancing the development of high-efficiency and high-brightness perovskite LEDs.

Interface Dipole Management of D-A-Type Molecules for Efficient Perovskite Solar Cells.

Interfacial engineering of perovskite films has been the main strategies in improving the efficiency and stability of perovskite solar cells (PSCs). In this study, three new donor-acceptor (D-A)-type interfacial dipole (DAID) molecules with hole-transporting and different anchoring units are designed and employed in PSCs. The formation of interface dipoles by the DAID molecules on the perovskite film can efficiently modulate the energy level alignment, improve charge extraction, and reduce non-radiative recombination. Among the three DAID molecules, TPA-BAM with amide group exhibits the best chemical and optoelectrical properties, achieving a champion PCE of 25.29 % with the enhanced open-circuit voltage of 1.174 V and fill factor of 84.34 %, due to the reduced defect density and improved interfacial hole extraction. Meanwhile, the operational stability of the unencapsulated device has been significantly improved. Our study provides a prospect for rationalized screening of interfacial dipole materials for efficient and stable PSCs.

Efficient Homojunction Tin Perovskite Solar Cells Enabled by Gradient Germanium Doping.

P-type self-doping is known to hamper tin-based perovskites for developing high-performance solar cells by increasing the background current density and carrier recombination processes. In this work, we propose a gradient homojunction structure with germanium doping that generates an internal electric field across the perovskite film to deplete the charge carriers. This structure reduces the dark current density of perovskite by over 2 orders of magnitude and trap density by an order of magnitude. The resultant tin-based perovskite solar cells exhibit a higher power conversion efficiency of 13.3% and excellent stability, maintaining 95% and 85% of their initial efficiencies after 250 min of continuous illumination and 3800 h of storage, respectively. We reveal the homojunction formation mechanism using density functional theory calculations and molecular level characterizations. Our work provides a reliable strategy for controlling the spatial energy levels in tin perovskite films and offers insights into designing intriguing lead-free perovskite optoelectronics.

Dualistic insulator states in 1T-TaS2 crystals.

While the monolayer sheet is well-established as a Mott-insulator with a finite energy gap, the insulating nature of bulk 1T-TaS2 crystals remains ambiguous due to their varying dimensionalities and alterable interlayer coupling. In this study, we present a unique approach to unlock the intertwined two-dimensional Mott-insulator and three-dimensional band-insulator states in bulk 1T-TaS2 crystals by structuring a laddering stack along the out-of-plane direction. Through modulating the interlayer coupling, the insulating nature can be switched between band-insulator and Mott-insulator mechanisms. Our findings demonstrate the duality of insulating nature in 1T-TaS2 crystals. By manipulating the translational degree of freedom in layered crystals, our discovery presents a promising strategy for exploring fascinating physics, independent of their dimensionality, thereby offering a "three-dimensional" control for the era of slidetronics.

A Catalyst-Like System Enables Efficient Perovskite Solar Cells.

High-quality perovskite films are essential for achieving high performance of optoelectronic devices; However, solution-processed perovskite films are known to suffer from compositional and structural inhomogeneity due to lack of systematic control over the kinetics during the formation. Here, the microscopic homogeneity of perovskite films is successfully enhanced by modulating the conversion reaction kinetics using a catalyst-like system generated by a foaming agent. The chemical and structural evolution during this catalytic conversion is revealed by a multimodal synchrotron toolkit with spatial resolutions spanning many length scales. Combining these insights with computational investigations, a cyclic conversion pathway model is developed that yields exceptional perovskite homogeneity due to enhanced conversion, having a power conversion efficiency of 24.51% for photovoltaic devices. This work establishes a systematic link between processing of precursor and homogeneity of the perovskite films.

Self-Polymerized Spiro-Type Interfacial Molecule toward Efficient and Stable Perovskite Solar Cells.

In the pursuit of highly efficient perovskite solar cells, spiro-OMeTAD has demonstrated recorded power conversion efficiencies (PCEs), however, the stability issue remains one of the bottlenecks constraining its commercial development. In this study, we successfully synthesize a novel self-polymerized spiro-type interfacial molecule, termed v-spiro. The linearly arranged molecule exhibits stronger intermolecular interactions and higher intrinsic hole mobility compared to spiro-OMeTAD. Importantly, the vinyl groups in v-spiro enable in situ polymerization, forming a polymeric protective layer on the perovskite film surface, which proves highly effective in suppressing moisture degradation and ion migration. Utilizing these advantages, poly-v-spiro-based device achieves an outstanding efficiency of 24.54 %, with an enhanced open-circuit voltage of 1.173 V and a fill factor of 81.11 %, owing to the reduced defect density, energy level alignment and efficient interfacial hole extraction. Furthermore, the operational stability of unencapsulated devices is significantly enhanced, maintaining initial efficiencies above 90 % even after 2000 hours under approximately 60 % humidity or 1250 hours under continuous AM 1.5G sunlight exposure. This work presents a comprehensive approach to achieving both high efficiency and long-term stability in PSCs through innovative interfacial design.

High-Performance Blue Perovskite Light-Emitting Diodes Enabled by Synergistic Effect of Additives.

While quasi-two-dimensional (quasi-2D) perovskites have good properties of cascade energy transfer, high exciton binding energy, and high quantum efficiency, which will benefit high-efficiency blue PeLEDs, inefficient domain distribution management and unbalanced carrier transport impede device performance improvement. Herein, (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz) and methyl 2-aminopyridine-4-carboxylate (MAC) were simultaneously introduced to a blue quasi-2D perovskite film. Relying on the synergistic effect of 2PACz and MAC, it not only modulates the phase distribution inhibiting the n = 2 phase but also greatly improves the electrical property of the quasi-2D perovskite film. As a result, the as-modified blue quasi-2D PeLED demonstrated an external quantum efficiency (EQE) of 17.08% and a luminance of 10142 cd m-2. This study exemplifies the synergistic effect among dual additives and offers a new effective additive strategy modulating phase distribution and building balanced carrier transport, which paves the way for the fabrication of highly efficient blue PeLEDs.

Polydentate Ligand Reinforced Chelating to Stabilize Buried Interface toward High-Performance Perovskite Solar Cells.

The instability of the buried interface poses a serious challenge for commercializing perovskite photovoltaic technology. Herein, we report a polydentate ligand reinforced chelating strategy to strengthen the stability of buried interface by managing interfacial defects and stress. The bis(2,2,2-trifluoroethyl) (methoxycarbonylmethyl)phosphonate (BTP) is employed to manipulate the buried interface. The C=O, P=O and two -CF3 functional groups in BTP synergistically passivate the defects from the surface of SnO2 and the bottom surface of the perovskite layer. Moreover, The BTP modification contributes to mitigated interfacial residual tensile stress, promoted perovskite crystallization, and reduced interfacial energy barrier. The multidentate ligand modulation strategy is appropriate for different perovskite compositions. Due to much reduced nonradiative recombination and heightened interface contact, the device with BTP yields a promising power conversion efficiency (PCE) of 24.63 %, which is one of the highest efficiencies ever reported for devices fabricated in the air environment. The unencapsulated BTP-modified devices degrade to 98.6 % and 84.2 % of their initial PCE values after over 3000 h of aging in the ambient environment and after 1728 h of thermal stress, respectively. This work provides insights into strengthening the stability of the buried interface by engineering multidentate chelating ligand molecules.

Crystallization Control Based on the Regulation of Solvent-Perovskite Coordination for High-Performance Ambient Printable FAPbI3 Perovskite Solar Cells.

The critical requirement for ambient-printed formamidinium lead iodide (FAPbI3 ) lies in the control of nucleation-growth kinetics and defect formation behavior, which are extensively influenced by interactions between the solvent and perovskite. Here, a strategy is developed that combines a cosolvent and an additive to efficiently tailor the coordination between the solvent and perovskite. Through in situ characterizations, the direct crystallization from the sol-gel phase to α-FAPbI3 is illustrated. When the solvent exhibits strong interactions with the perovskite, the sol-gel phases cannot effectively transform into α-FAPbI3 , resulting in a lower nucleation rate and confined crystal growth directions. Consequently, it becomes challenging to fabricate high-quality void-free perovskite films. Conversely, weaker solvent-perovskite coordination promotes direct crystallization from sol-gel phases to α-FAPbI3 . This process exhibits more balanced nucleation-growth kinetics and restrains the formation of defects and microstrains in situ. This strategy leads to improved structural and optoelectronic properties within the FAPbI3 films, characterized by more compact grain stacking, smoother surface morphology, released lattice strain, and fewer defects. The ambient-printed FAPbI3 perovskite solar cells fabricated using this strategy exhibit a remarkable power conversion efficiency of 24%, with significantly reduced efficiency deviation and negligible decreases in the stabilized output.

Optimizing the Buried Interface in Flexible Perovskite Solar Cells to Achieve Over 24% Efficiency and Long-Term Stability.

The buried interface of the perovskite layer has a profound influence on its film morphology, defect formation, and aging resistance from the outset, therefore, significantly affects the film quality and device performance of derived perovskite solar cells. Especially for FAPbI3 , although it has excellent optoelectronic properties, the spontaneous transition from the black perovskite phase to nonperovskite phase tends to start from the buried interface at the early stage of film formation then further propagate to degrade the whole perovskite. In this work, by introducing ─NH3 + rich proline hydrochloride (PF) with a conjugated rigid structure as a versatile medium for buried interface, it not only provides a solid α-phase FAPbI3 template, but also prevents the phase transition induced degradation. PF also acts as an effective interfacial stress reliever to enhance both efficiency and stability of flexible solar cells. Consequently, a champion efficiency of 24.61% (certified 23.51%) can be achieved, which is the highest efficiency among all reported values for flexible perovskite solar cells. Besides, devices demonstrate excellent shelf-life/light soaking stability (advanced level of ISOS stability protocols) and mechanical stability.

Manipulation of Shallow-Trap States in Halide Double Perovskite Enables Real-Time Radiation Dosimetry.

Storage phosphors displaying defect emissions are indispensable in technologically advanced radiation dosimeters. The current dosimeter is limited to the passive detection mode, where ionizing radiation-induced deep-trap defects must be activated by external stimulation such as light or heat. Herein, we designed a new type of shallow-trap storage phosphor by controlling the dopant amounts of Ag+ and Bi3+ in the host lattice of Cs2NaInCl6. A distinct phenomenon of X-ray-induced emission (XIE) is observed for the first time in an intrinsically nonemissive perovskite. The intensity of XIE exhibits a quantitative relationship with the accumulated dose, enabling a real-time radiation dosimeter. Thermoluminescence and in situ X-ray photoelectron spectroscopy verify that the emission originates from the radiative recombination of electrons and holes associated with X-ray-induced traps. Theoretical calculations reveal the evolution process of Cl-Cl dimers serving as hole trap states. Analysis of temperature-dependent radioluminescence spectra provides evidence that the intrinsic electron-phonon interaction in 0.005 Ag+@ Cs2NaInCl6 is significantly reduced under X-ray irradiation. Moreover, 0.025 Bi3+@ Cs2NaInCl6 shows an elevated sensitivity to the accumulated dose with a broad response range from 0.08 to 45.05 Gy. This work discloses defect manipulation in halide double perovskites, giving rise to distinct shallow-trap storage phosphors that bridge traditional deep-trap storage phosphors and scintillators and enabling a brand-new type of material for real-time radiation dosimetry.

Intermediate Phase Free α-FAPbI3 Perovskite via Green Solvent Assisted Perovskite Single Crystal Redissolution Strategy.

Perovskite single-crystal redissolution (PSCR) strategy is highly desired for efficient formamidinium lead triiodide (FAPbI3 ) perovskite photovoltaics with enhanced phase purity, improved film quality, low trap-state density, and good stability. However, the phase transition and crystallization dynamics of FAPbI3 remain unclear in the PSCR process compared to the conventional fabrication from the mixing of precursor materials. In this work, a green-solvent-assisted (GSA) method is employed to synthesize centimeter-sized α-FAPbI3 single crystals, which serve as the high-purity precursor to fabricate perovskite films. The α-FAPbI3 PSCR strategy facilitates direct α-phase formation and inhibits the complex intermediate phases monitored by in situ grazing-incidence wide-angle X-ray scattering. Moreover, the α-phase stability is prolonged due to the relaxation of the residual lattice strain through the isotropic orientation phase growth. Consequently, the GSA-assisted PSCR strategy effectively promotes crystallization and suppresses non-radiative recombination in perovskite solar cells, which boosts the device efficiency from 22.08% to 23.92% with significantly enhanced open circuit voltage. These findings provide deeper insight into the PSCR process in terms of its efficacy in phase formation and lattice strain release. The green low-cost solvent may also offer a new and ideal solvent candidate for large-scale production of perovskite photovoltaics.

Crystallization Control for Ambient Printed FA-Based Lead Triiodide Perovskite Solar Cells.

Upscalable printing of high-performance and stable perovskite solar cells (PSCs) is highly desired for commercialization. However, the efficiencies of printed PSCs lag behind those of their lab-scale spin-coated counterparts owing to the lack of systematic understanding and control over perovskite crystallization dynamics. Here, the controlled crystallization dynamics achieved using an additive 1-butylpyridine tetrafluoroborate (BPyBF4 ) for high-quality ambient printed α-formamidinium lead triiodide (FAPbI3 ) perovskite films are reported. Using in situ grazing-incidence wide-angle X-ray scattering and optical diagnostics, the spontaneous formation of α-FAPbI3 from precursors during printing without the involvement of  Î´-FAPbI3 is demonstrated. The addition of BPyBF4 delays the crystallization onset of α-FAPbI3 , enhances the conversion from sol-gel to perovskite, and reduces stacking defects during printing. Therefore, the altered crystallization results in fewer voids, larger grains, and less trap-induced recombination loss within printed films. The printed PSCs yield high power conversion efficiencies of 23.50% and 21.60% for a 0.09 cm-2 area device and a 5 cm × 5 cm-area module, respectively. Improved device stability is further demonstrated, i.e., approximately 94% of the initial efficiency is retained for over 2400 h under ambient conditions without encapsulation. This study provides an effective crystallization control method for the ambient printing manufacture of large-area high-performance PSCs.