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At least 1,297 records · Page 72

Measuring the Exciton Binding Energy: Learning from a Decade of Measurements on Halide Perovskites and Transition Metal Dichalcogenides

The exciton binding energy ( E b ) is a key parameter that governs the physics of many optoelectronic devices. At their best, trustworthy and precise measurements of E b challenge theoreticians to refine models, are a driving force in advancing the understanding of a material system, and lead to efficient device design. At their worst, inaccurate E b measurements lead theoreticians astray, sow confusion within the research community, and hinder device improvements by leading to poor designs. Here, this review article seeks to highlight the pros and cons of different measurement techniques used to determine E b , namely, temperature‐dependent photoluminescence, resolving Rydberg states, electroabsorption, magnetoabsorption, scanning tunneling spectroscopy, and fitting the optical absorption. Due to numerous conflicting E b values reported for halide perovskites (HP) and transition metal dichalcogenides (TMDC) monolayers, an emphasis is placed on highlighting these measurements in an attempt to reconcile the variance between different measurement techniques. It is argued that the experiments with the clearest indicators are in agreement on the following values: ≈350–450 meV for TMDC monolayers between SiO 2 and vacuum, ≈150–200 meV for hBN‐encapsulated TMDC monolayers, ≈200–300 meV for common lead‐iodide 2D HPs, and ≈10 meV for methylammonium lead iodide.

36 MATERIALS SCIENCE↗

Impact of Halogen Groups on the Properties of PEA–Based 2D Pb–Sn Halide Perovskites

Tuning broad emission in 2D Pb–Sn halide perovskites (HPs) is essential for advancing optoelectronic applications, particularly for color-tunable and white-light-emitting devices. This broad emission is linked to structural factors, such as defects and phase segregation of the Pb component within the Pb–Sn system, which are strongly influenced by the molecular structure and chemical properties of spacer cations. Atomic tuning of the spacers via halogenation opens up a new way to fine-tune the molecular properties, enabling further augmentations of HP functionalities. Nevertheless, the distinct broad emission's sensitivity to spacer chemistry remains underexplored. Here, halogenation's influence is systematically investigated on 2D HP emission characteristics using a high-throughput workflow. These findings reveal that the F-containing phenethylammonium (4F-PEA) spacer narrows the broadband PL, whereas Cl broadens it. Through a correlative study, it is found that 4F-PEA reduces not only the local phase segregation but also the defect levels and microstrains in 2D HPs. This is likely attributed to the manifestation of less lattice distortion via stronger surface coordination of the dipole-augmented 4F-PEA. Furthermore, these results highlight halogenation as a key factor in modulating phase segregation and defect density in 2D Pb–Sn HPs, offering a promising pathway to tune the emission for enhanced optoelectronic performance.

2D Pb-Sn halide perovskites↗

Pressure‐Induced Structural and Optoelectronic Modulations in 2D Dion‐Jacobson Hybrid Lead Iodide Perovskites With a Rigid Spacer

2D hybrid organic-inorganic perovskites (HOIPs) are known for their superior chemical and thermal stability over 3D variants, positioning them as promising materials for advanced optoelectronic applications. Applying external high pressure is an effective strategy to modify their structures and tune their optoelectronic properties. This study examines the high-pressure behavior of a Dion-Jacobson type 2D HOIP, DPDAPbI 4 , which incorporates the rigid organic spacer N,N-dimethylphenylene-p-diammonium (DPDA). Utilizing photoluminescence, UV–visible absorption, vibrational spectroscopy, and in situ synchrotron powder X-ray diffraction, an isostructural phase transition is identified near 1.5 GPa, marked by a notable shift in photoluminescence intensity linked to free exciton emission. Synchrotron X-ray diffraction reveals significant anisotropic compression along the c-axis, while structural analysis indicates the rare phenomenon of reduced lead-iodide octahedral distortion below 2 GPa, contrasting with the increased octahedral distortion reported in most previous studies on lead-based 2D HOIPs. Density functional theory calculations elucidate the structural origins and mechanisms driving the pressure-induced phase transition and optoelectronic tuning. These findings underscore the critical interplay between rigid organic spacers and inorganic octahedra in modulating high-pressure optoelectronic properties, offering valuable insights for designing future 2D HOIPs with tailored functionalities.

14 SOLAR ENERGY↗

Experimental Evidence of Free Carrier Generation in 2D Hybrid Organic–Inorganic Perovskites

Despite the significant potential of 2D hybrid organic–inorganic perovskites (2DHOIPs) for high-efficiency optoelectronics application-comparable to their 3D counterparts, the fundamental carrier photogeneration remains unclear. In contrast to conventional ultrafast optical property characterization, we use ultrafast photocurrent spectroscopy to investigate the early-time electrical properties of type-I and type-II 2DHOIPs by manipulating the quantum confinement and the dielectric quantum matching effect. We discovered that the high frequency dielectric quantum matching effect plays a major role in 2DHOIPs, demonstrated by their high carrier mobility (µ), near-unity photogeneration quantum yield (Φ), below-room temperature exciton binding energy (E b ), and approaching 3D space factor (DSF). Our work shows that the optoelectronic performances of 2DHOIPs are comparable to their counterparts of 3DHOIPs.

2D perovskite↗

Cesium Lead Halide Perovskite Nanocrystals Assembled in Metal–Organic Frameworks for Stable Blue Light Emitting Diodes

All inorganic cesium lead trihalide nanocrystals are promising light emitters for bright light emitting diodes (LEDs). Here we demonstrate CsPb(BrCl) 1.5 nanocrystals in metal-organic frameworks (MOF) thin films to achieve bright and stable blue LEDs. The lead metal nodes in the MOF thin film react with Cs-halide salts, resulting in 10~20 nm nanocrystals. This is revealed by X-ray scattering and transmission electron microscopy. Employing the CsPbX 3 - MOF thin films as emission layers, bright deep blue and sky-blue LEDs are demonstrated that emit at 452 nm and 476 nm respectively. The maximum external quantum efficiencies of these devices are 0.72% for deep blue LEDs and 5.6% for sky blue LEDs. More importantly, the device can maintain 50% of its original electroluminescence (T 50 ) for 2.23 hours when driving at 4.2V. Detailed optical spectroscopy and time-of-flight secondary ion mass spectroscopy suggest that the ion migration can be suppressed that maintains the emission brightness and spectra. Our study provides a new route for fabricating stable blue light emitting diodes with all-inorganic perovskite nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Organometal Halide Perovskite‐Based Photoelectrochemical Module Systems for Scalable Unassisted Solar Water Splitting

Despite achievements in the remarkable photoelectrochemical (PEC) performance of photoelectrodes based on organometal halide perovskites (OHPs), the scaling up of small-scale OHP-based PEC systems to large-scale systems remains a great challenge for their practical application in solar water splitting. Significant resistive losses and intrinsic defects are major obstacles to the scaling up of OHP-based PEC systems, leading to the PEC performance degradation of large-scale OHP photoelectrodes. Herein, a scalable design of the OHP-based PEC systems by modularization of the optimized OHP photoelectrodes exhibiting a high solar-to-hydrogen conversion efficiency of 10.4% is suggested. As a proof-of-concept, the OHP-based PEC module achieves an optimal PEC performance by avoiding major obstacles in the scaling up of the OHP photoelectrodes. The constructed OHP module is composed of a total of 16 OHP photoelectrodes, and a photocurrent of 11.52 mA is achieved under natural sunlight without external bias. The successful operation of unassisted solar water splitting using the OHP module without external bias can provide insights into the design of scalable OHP-based PEC systems for future practical application and commercialization.

14 SOLAR ENERGY↗

Strain–Chemical Gradient and Polarization in Metal Halide Perovskites

Metal halide perovskites (MHPs) have attracted broad research interest due to their outstanding optoelectronic performance. This performance has been attributed in part to the presence of polarization in these materials. However, the precise effects of chemical environment and strain condition on the polar states in MHPs have largely been missing. Herein it is revealed for the first time that chemical gradient is directly coupled with strain gradient in CH 3 NH 3 PbI 3 . This strain–chemical gradient induces an electric polarization that can potentially affect charge carrier dynamics. Furthermore, it is unveiled that this electric polarization—unlike ferroelectricity that only exists in noncentrosymmetric materials—can be present in both tetragonal and cubic phases of CH 3 NH 3 PbI 3 . This suggests that the strain–chemical gradient induced polarization is a more convincing explanation of the outstanding photovoltaic properties of MHPs than the hotly debated ferroelectric polarization. Finally, a mechanism of how this polarization impacts photovoltaic action is proposed, which offers insightful advances in the development of MHPs.

36 MATERIALS SCIENCE↗

Development and Prospects of Halide Perovskite Single Crystal Films

Halide perovskite single crystal (HPSC) films have demonstrated extraordinary performance in solar cells, photodetectors, and lighting applications, owing to the high carrier mobility, long carrier diffusion length, tunable bandgap, and large light absorption coefficients of these materials. Here, the recent development of the major HPSC thin films is reviewed systematically, including MAPbI 3 , α-FAPbI 3 , MAPbBr 3 , CsPbBr 3 , with special emphasis on different classes of fabrication methods and thin-film characteristics. So finally, the conclusion and prospects in this field are discussed in detail. It is anticipated that the HPSC thin films will lead to a compelling future for the rising electronic applications.

MAPbI3↗

Investigating the Effects of Chemical Gradients on Performance and Reliability within Perovskite Solar Cells with TOF-SIMS

Time-of-flight secondary-ion mass spectrometry (TOF-SIMS), a powerful analytical technique sensitive to all components of perovskite solar cell (PSC) materials, can differentiate between the various organic species within a PSC absorber or a complete device stack. The ability to probe chemical gradients through the depth of a device (both organic and inorganic), with down to 100 nm lateral resolution, can lead to unique insights into the relationships between chemistry in the absorber bulk, at grain boundaries, and at interfaces as well as how they relate to changes in performance and/or stability. In this essay, the technique is described; then, from the literature, several examples of how TOF-SIMS have been used to provide unique insight into PSC absorbers and devices are covered. Finally, the common artifacts that can be introduced if the data are improperly collected, as well as methods to mitigate these artifacts are discussed.

14 SOLAR ENERGY↗

The Value of Watching How Materials Grow: A Multimodal Case Study on Halide Perovskites

Material synthesis is one of the most important aspects in humankinds’ endeavor to discover and create new materials for energy applications. One strategy to tailor materials with desired functions in a rational way is by knowing how functions relate to structure, synthetic variables, arrangement of atoms and molecules, and how functions evolve during synthesis. In order to accelerate materials synthesis, discovery, and optimization by 10 times it is the right time now to integrate computational tools, synthesis, and characterization. One particular barrier to realizing this concept is the understanding of when and how phases form in real time during synthesis, which is challenging to asses by existing theoretical frameworks. In addition, transient or metastable phases with positive free energy above the lowest-free energy ground state can be revealed by such real time (in situ) measurements. Metastable materials are ubiquitous in condensed matter and can show superior properties compared to their equilibrium form. This work discusses the value of emerging multimodal in situ characterizations exemplified on hybrid halide perovskites. Finally, the ways in which the implementation of in situ measurements can advance the materials science synthesis field as well as their role to enable close-loop feedback control and autonomous synthesis are discussed.

36 MATERIALS SCIENCE↗

Comprehensive Performance Calibration Guidance for Perovskites and Other Emerging Solar Cells

Emerging photovoltaic (PV) technologies (e.g., organic, perovskite, and solution processed quantum dot) have attracted remarkable attention with the rapid growth of their efficiencies, and their transition toward commercialization. Accurate and reliable efficiency measurements of these PV technologies are crucial, yet much more complicated than for conventional PV technologies due to the former's pronounced dynamic responses to changes in measurement conditions (e.g., current–voltage (I–V) scan rate and preconditioning) and their susceptibility to degradation. Adjustments to the measurement procedures are therefore necessary so that a reproducible “steady state” is reached during measurement. Furthermore, given the small size of many emerging cells, inappropriate device area definition and solar simulator setup can lead to measurement errors. Here, comprehensive efficiency calibration guidance is offered for emerging solar cells, including area measurement; spectral irradiance translation to standard test conditions; and steady-state electrical performance. The necessity of reporting steady-state efficiency is justified with a statistical performance comparison between conventional and steady-state I–V scans over hundreds of cells the group has received globally for efficiency certifications. The procedures described here do not require specialized measurement instrumentation; what matters most are changes to the measurement protocols. These described changes aim to enable better comparisons between reported efficiencies.

14 SOLAR ENERGY↗

Revealing the Transient Formation Dynamics and Optoelectronic Properties of 2D Ruddlesden–Popper Phases on 3D Perovskites

Using in situ photoluminescence measurements during the spin-coating and annealing steps, this study probes the formation of 2D layers on 3D triple cation perovskite films comparing phenylethylammonium and 2-thiophenemethylammonium iodide bulky cations. This study elucidates the formation mechanisms of the surface layers for both cases and reveals two regimes during 2D layer formation: a kinetic-driven and a thermodynamic-driven process. These driving forces result in different compositions of the 2D/3D interface for each treatment, namely, different ratios of pure 2D (n = 1) and quasi-2D (n > 1) structures. Further, this study shows that a higher ratio of quasi-2D phases is more beneficial for device performance, as pure-2D layers may hamper current extraction. Due to a more evenly distributed formation energy profile among 2D and quasi-2D phases, highly concentrated 2-thiophenemethylammonium iodide appears to be more suited for effective surface passivation than its phenylethylammonium analog.

36 MATERIALS SCIENCE↗

Direct Characterization of Type-I Band Alignment in 2D Ruddlesden–Popper Perovskites

2D Ruddlesden–Popper halide perovskites have attracted considerable attention due to their desirable optoelectronic properties, high chemical and structural tunability, and improved environmental stability. However, the understanding of their structure–properties relationships is still limited. In particular, the energy level positions and band alignments at interfaces involving these materials, which are important features to control in the context of any applications, are still under debate. Here, the electronic structure of high-purity films of BA 2 MA n-1 Pb n I 3n+1 for n = 1–5 (where BA stands for butylammonium and MA for methylammonium) is investigated, using optical absorption, ultraviolet, and inverse photoemission spectroscopies, and density functional theory calculations. Further, this study determines the ionization energy and electron affinity of each compound and demonstrates a type-I band alignment for the BA 2 MA n-1 Pb n I 3n+1 series. This study further describes the evolution of the exciton binding energy as a function of the thickness of the inorganic layers.

2D Ruddlesden–Popper perovskites↗

Chemical Design of Organic Interface Modifiers for Highly Efficient and Stable Perovskite Solar Cells

Perovskite solar cells (PSCs) have demonstrated rapid progress in their power conversion efficiencies (PCEs) - from 3.8% in 2009 to 25.7% in 2022 - and they have received considerable attention as a promising future photovoltaic (PV) technology. However, the operational stability of PSCs is still inadequate to satisfy the standards for commercial applications. Interface engineering has become one of the most important strategies to push PSCs' efficiency and stability for practical use. Among the various interface engineering approaches, organic interface modifiers (OIMs) have been frequently used by the PSC field to address the issues limiting PSC stability at high efficiency levels. In this perspective, the chemical structures of state-of-the-art OIMs are discussed, and their characteristics are reviewed, as well as the impact on device performance associated with key device interfaces (e.g., metal oxide/perovskite and organic transport layer/perovskite interfaces) from a chemical and materials engineering point of view is discussed. Finally, design considerations and the authors' perspective are discussed, on the basis of representative literature examples, for building new, customized organic OIMs to further improve PSC efficiency and stability toward commercialization.

14 SOLAR ENERGY↗

Light–Induced Frenkel Defect Pair Formation Can Lead to Phase–Segregation of Otherwise Miscible Halide Perovskite Alloys

Alloys of ABX 3 halide perovskites (HP) exhibit unique phase behavior compared to traditional III-V and II-VI semiconductor alloys used in solar cells. While the latter typically have good mutual miscibility when their mixed components are size matched, and phase-segregate when size mismatched, HP alloys show good miscibility in the dark but can phase-segregate under light. Quantum mechanical calculations described herein reveal light-induced defect formation and migration hold the key. Specifically, the interaction between a halogen vacancy V X with halogen interstitial X i forming together a Frenkel-pair defect emerges as the enabler for phase-segregation in HP alloys. At a threshold bromine composition in the Br-I alloys, the photogenerated holes in the valence band localize, creating thereby a doubly-charged iodine Frenkel-pair (V I + I i ) 2+ . Faster migration of iodine over bromine interstitial into the vacant iodine V I site leads to the formation of iodine-rich and iodine-depleted regions, establishing phase-segregation. Removal of the mobile defects–the agent of segregation–by dark thermal annealing, supplies the opposing force, leading to reversal of phase-segregation. Furthermore, this atomistic understanding can enable some control of the phase-segregation by selecting substituting elements on the B site–such as replacing some Pb by Sn–that are unable to form stable Frenkel defects.

14 SOLAR ENERGY↗

High-Throughput Automated Exploration of Phase Growth Behaviors in Quasi-2D Formamidinium Metal Halide Perovskites

Quasi-2D metal halide perovskites (MHPs) are an emerging material platform for sustainable functional optoelectronics, but the uncontrollable, broad phase distribution remains a critical challenge for applications. Nevertheless, the basic principles for controlling phases in quasi-2D MHPs remain poorly understood, due to the rapid crystallization kinetics during the conventional thin-film fabrication process. In this work, a high-throughput automated synthesis-characterization-analysis workflow is implemented to accelerate material exploration in formamidinium (FA)-based quasi-2D MHP compositional space, revealing the early-stage phase growth behaviors fundamentally determining the phase distributions. Upon comprehensive exploration with varying synthesis conditions including 2D:3D composition ratios, antisolvent injection rates, and temperatures in an automated synthesis-characterization platform, it is observed that the prominent n = 2 2D phase restricts the growth kinetics of 3D-like phases—α-FAPbI 3 MHPs with spacer-coordinated surface—across the MHP compositions. Thermal annealing is a critical step for proper phase growth, although it can lead to the emergence of unwanted local PbI 2 crystallites. Additionally, fundamental insights into the precursor chemistry associated with spacer-solvent interaction determining the quasi-2D MHP morphologies and microstructures are demonstrated. The high-throughput study provides comprehensive insights into the fundamental principles in quasi-2D MHP phase control, enabling new control of the functionalities in complex materials systems for sustainable device applications.

2D perovskites↗

Field‐Relevant Degradation Mechanisms in Metal Halide Perovskite Modules

Field testing, failure analysis, and understanding of degradation mechanisms are essential to advancing metal halide perovskite (MHP) photovoltaic (PV) technology toward commercialization. Here, we present performance data from up to 1 year of outdoor testing of MHP modules in Golden, Colorado. The module encapsulation architecture and encapsulant materials have a significant impact on module reliability, with modules containing a polyolefin elastomer (POE) in addition to a desiccated polyisobutylene (PIB) edge seal outlasting modules with only a PIB edge seal or PIB blanket. Nondestructive and destructive characterization of the field-tested modules points to module scribes and interfaces as areas of potential mechanical weakness and chemical migration, resulting in shunt pathways and increased series resistance. Finally, indoor accelerated stress testing with light and elevated temperatures is performed, demonstrating failure with similar scribe degradation signatures as compared to the field-tested modules. In conclusion, under both outdoor testing and light and elevated temperature conditions, electrochemical corrosion between the copper electrode and the mobile iodine ions appeared dominant, with a significant progression at the scribes that is speculated to result from an interplay between the initial laser damage and joule heating from enhanced ion diffusion under bias.

14 SOLAR ENERGY↗

Tailoring Molecular Space to Navigate Phase Complexity in Cs-Based Quasi-2D Perovskites via Gated-Gaussian-Driven High-Throughput Discovery

Cesium-based quasi-2D halide perovskites (HPs) offer promising functionalities and low-temperature manufacturability, suited to stable tandem photovoltaics. However, the chemical interplays between the molecular spacers and the inorganic building blocks during crystallization cause substantial phase complexities in the resulting matrices. To successfully optimize and implement the quasi-2D HP functionalities, a systematic understanding of spacer chemistry, along with the seamless navigation of the inherently discrete molecular space, is necessary. Herein, by utilizing high-throughput automated experimentation, the phase complexities in the molecular space of quasi-2D HPs are explored, thus identifying the chemical roles of the spacer cations on the synthesis and functionalities of the complex materials. Furthermore, a novel active machine learning algorithm leveraging a two-stage decision-making process, called gated Gaussian process Bayesian optimization is introduced, to navigate the discrete ternary chemical space defined with two distinctive spacer molecules. Through simultaneous optimization of photoluminescence intensity and stability that “tailors” the chemistry in the molecular space, a ternary-compositional quasi-2D HP film realizing excellent optoelectronic functionalities is demonstrated. Finally, this work not only provides a pathway for the rational and bespoke design of complex HP materials but also sets the stage for accelerated materials discovery in other multifunctional systems.

36 MATERIALS SCIENCE↗