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Amassian, Aram

Publications and source records attributed to Amassian, Aram.

Why Perovskite Thermal Stress is Unaffected by Thin Contact Layers

Metal halide perovskite photovoltaics have emerged as a high efficiency, low-cost alternative that can potentially rival or enhance conventional silicon technology. Despite exceptional initial power conversion efficiencies, achieving compliance with international standards and widespread adoption requires further enhancements to their operational stability. Notably, addressing mechanical strain and stress in brittle perovskites has emerged as a pivotal approach to mitigate chemical degradation and improve reliability during thermal cycling. Here, in this study, a popularized strain engineering strategy is investigated in which a high coefficient of thermal expansion (CTE) hole transport layer (i.e., PDCBT) is cast onto inorganic perovskite (CsPbI 2 Br) at 100 °C. Contrary to previously published results, the X-ray diffraction (XRD):Sin 2 ψ and substrate curvature measurement techniques show that the hole transport layer has no discernible impact on perovskite strain. The accuracy of the XRD:Sin 2 ψ method for measuring strain is highlighted in contrast to an analysis based on shifts of single XRD peaks which can be influenced by multiple artifacts. The findings in this study are in accordance with mechanics theory: thin layers are unable to induce significant strain changes in perovskite thin films as the force they apply is negligible compared to that applied by a thick and stiff substrate.

14 SOLAR ENERGY↗

In situ Stress Monitoring Reveals Tension and Wrinkling Evolutions during Halide Perovskite Film Formation

Metal halide perovskites (MHPs) are promising candidates for next-generation thin film photovoltaics and high-performance tandems. Solution-processed MHP films are susceptible to residual stress that can induce undesirable surface wrinkles. However, the origins and evolution of stress during solution processing remain elusive. Here, in this work, we utilize multimodal in situ characterizations, including substrate curvature, reflectance, absorbance, and photoluminescence, to monitor stress and morphology evolution during MHP film formation. A film formation model emerges, consisting of a perovskite top crust on a semirigid sol with the ability to transfer mechanical forces. The phase transformation induces tension in the MHP crust, while shrinkage of the sol causes additional compression and surface wrinkles. Wrinkle-free films are formed through dynamically balancing forces between the crust and the sol. This study provides a powerful toolkit for the fast-growing area of stress engineering in MHP photovoltaics to achieve dynamic control of film stress and surface morphology.

36 MATERIALS SCIENCE↗

Sustainable materials acceleration platform reveals stable and efficient wide-bandgap metal halide perovskite alloys

The vast chemical space of emerging semiconductors, like metal halide perovskites, and their varied requirements for semiconductor applications have rendered trial-and-error environmentally unsustainable. Here, in this work, we demonstrate RoboMapper, a materials acceleration platform (MAP), that achieves 10-fold research acceleration by formulating and palletizing semiconductors on a chip, thereby allowing high-throughput (HT) measurements to generate quantitative structure-property relationships (QSPRs) considerably more efficiently and sustainably. We leverage the RoboMapper to construct QSPR maps for the mixed ion FA 1-y Cs y Pb(I 1-x Br x ) 3 halide perovskite in terms of structure, bandgap, and photostability with respect to its composition. We identify wide-bandgap alloys suitable for perovskite-Si hybrid tandem solar cells exhibiting a pure cubic perovskite phase with favorable defect chemistry while achieving superior stability at the target bandgap of ~1.7 eV. RoboMapper’s palletization strategy reduces environmental impacts of data generation in materials research by more than an order of magnitude, paving the way for sustainable data-driven materials research.

36 MATERIALS SCIENCE↗

Engineering ligand reactivity enables high-temperature operation of stable perovskite solar cells

Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. Here, we found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi–steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hour T85 at maximum power point under 1-sun illumination.

14 SOLAR ENERGY↗

Interactions between nonfullerene acceptors lead to unstable ternary organic photovoltaic cells

For organic photovoltaic (OPV) devices to achieve consistent performance and long operational lifetimes, organic semiconductors must be processed with precise control over their purity, composition, and structure. This is particularly important for high volume solar cell manufacturing where control of materials quality has a direct impact on yield and cost. Ternary-blend OPVs containing two acceptor–donor–acceptor (A–D–A)-type nonfullerene acceptors (NFAs) and a donor have proven to be an effective strategy to improve solar spectral coverage and reduce energy losses beyond that of binary-blend OPVs. Here, we show that the purity of such a ternary is compromised during blending to form a homogeneously mixed bulk heterojunction thin film. We find that the impurities originate from end-capping C=C/C=C exchange reactions of A–D–A-type NFAs, and that their presence influences both device reproducibility and long-term reliability. The end-capping exchange results in generation of up to four impurity constituents with strong dipolar character that interfere with the photoinduced charge transfer process, leading to reduced charge generation efficiency, morphological instabilities, and an increased vulnerability to photodegradation. As a consequence, the OPV efficiency falls to less than 65% of its initial value within 265 h when exposed to up to 10 suns intensity illumination. We propose potential molecular design strategies critical to enhancing the reproducibility as well as reliability of ternary OPVs by avoiding end-capping reactions.

14 SOLAR ENERGY↗

A universal co-solvent dilution strategy enables facile and cost-effective fabrication of perovskite photovoltaics

Cost management and toxic waste generation are two key issues that must be addressed before the commercialization of perovskite optoelectronic devices. We report a groundbreaking strategy for eco-friendly and cost-effective fabrication of highly efficient perovskite solar cells. This strategy involves the usage of a high volatility co-solvent, which dilutes perovskite precursors to a lower concentration (<0.5 M) while retaining similar film quality and device performance as a high concentration (>1.4 M) solution. More than 70% of toxic waste and material cost can be reduced. Mechanistic insights reveal ultra-rapid evaporation of the co-solvent together with beneficial alteration of the precursor colloidal chemistry upon dilution with co-solvent, which in-situ studies and theoretical simulations confirm. The co-solvent tuned precursor colloidal properties also contribute to the enhancement of the stability of precursor solution, which extends its processing window thus minimizing the waste. This strategy is universally successful across different perovskite compositions, and scales from small devices to large-scale modules using industrial spin-coating, potentially easing the lab-to-fab translation of perovskite technologies.

36 MATERIALS SCIENCE↗

Observation of spatially resolved Rashba states on the surface of CH 3 NH 3 PbBr 3 single crystals

Hybrid organic-inorganic perovskites (HOIPs) are prime candidates for studying Rashba effects due to the heavy metal and halogen atoms in their crystal structure coupled with predicted inversion symmetry breaking. Nevertheless, observation of the Rashba effect in cubic CH 3 NH 3 PbBr 3 single crystals that possess bulk inversion symmetry is the subject of extensive debate due to the lack of conclusive experiments and theoretical explanations. In this work, we provide experimental evidence that Rashba state in cubic CH 3 NH 3 PbBr 3 single crystals at room temperature occurs exclusively on the crystal surface and depends on specific surface termination that results in local symmetry breaking. We demonstrate this using a suite of spatially resolved and depth-sensitive techniques, including circular photogalvanic effect, inverse spin Hall effect, and multiphoton microscopy, that are supported by first principle calculations. Our work suggests using surface Rashba states in these materials for spintronic applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Colloidal Quantum Dot Photovoltaics: Current Progress and Path to Gigawatt Scale Enabled by Smart Manufacturing

Colloidal quantum dots (QDs) have lately been pursued with intense vigor for optoelectronic applications such as photovoltaics (PV), flexible electronics, displays, mid-infrared photodetectors, lasers, and single-photon emitters. These nanometer-sized semiconducting crystals can be suitably mass-produced and size-tuned via cost-effective solution-based synthetic routes to operate in the quantum size confinement regime, endowing them with a wide array of exotic optical and electronic properties. While the first potential market entry could be in displays and in niche applications such as “internet-of-things”, ultimately, the technology has the potential to influence large-scale terrestrial power generation, because it is amenable to high-throughput synthesis from Earth-abundant materials and large-area solution-based coating techniques and can be air-stable. In this Review, we chronicle the recent advances that have propelled QD PV toward commercialization and highlight potential areas for further progress. We present an account of the material compositions being explored as QDs and their various benefits, major chemical passivation and doping strategies that have been developed to allay QD surface traps, and advanced device designs deployed to maximize charge extraction. We also discuss pathways to >20% efficient QD PV and describe recent advances in high-precision and autonomous synthesis of such materials. With recent demonstrations of scalable synthesis of high-quality QDs, smart manufacturing of QDs and QD solids, and fabrication of stable solar cells under ambient conditions, we suggest that the technology is on the road to achieving maturity and technological relevance and that gigawatt per year distributed panel production sites may be within reach.

14 SOLAR ENERGY↗

Critical Role of Polymer Aggregation and Miscibility in Nonfullerene‐Based Organic Photovoltaics

Abstract Understanding the correlation between polymer aggregation, miscibility, and device performance is important to establish a set of chemistry design rules for donor polymers with nonfullerene acceptors (NFAs). Employing a donor polymer with strong temperature‐dependent aggregation, namely PffBT4T‐2OD [poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐ alt ‐(3,3″′‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2″′‐quaterthiophen‐5,5‐diyl)], also known as PCE‐11 as a base polymer, five copolymer derivatives having a different thiophene linker composition are blended with the common NFA O‐IDTBR to investigate their photovoltaic performance. While the donor polymers have similar optoelectronic properties, it is found that the device power conversion efficiency changes drastically from 1.8% to 8.7% as a function of thiophene content in the donor polymer. Results of structural characterization show that polymer aggregation and miscibility with O‐IDTBR are a strong function of the chemical composition, leading to different donor–acceptor blend morphology. Polymers having a strong tendency to aggregate are found to undergo fast aggregation prior to liquid–liquid phase separation and have a higher miscibility with NFA. These properties result in smaller mixed donor–acceptor domains, stronger PL quenching, and more efficient exciton dissociation in the resulting cells. This work indicates the importance of both polymer aggregation and donor–acceptor interaction on the formation of bulk heterojunctions in polymer:NFA blends.

Yi, Xueping↗