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At least 1,225 records · Page 68

Integrating Advanced Modeling and Accelerated Testing for a Modernized Fuel Qualification Paradigm

With the increasing interest in sodium fast reactor technology, as seen by applications to the U.S. Nuclear Regulatory Commission for the OKLO Aurora plant, fuel testing for the TerraPower Traveling Wave Reactor, and the impending construction and startup of the versatile test reactor (VTR), a modernized, accelerated approach to fuel qualification is needed. To guide this effort, a Phenomena Identification Ranking Table–styled analysis was performed for a U-Pu-Zr sodium-free annular fuel system. This analysis evaluated a series of fuel design properties and parameters against their contributions to key fuel performance phenomena. The resulting priority parameters were then reviewed against existing modeling and experimental capabilities to support investigation of the highest-priority parameters. A pathway for qualification was then established using highthroughput, high-volume experiments from MiniFuel and FAST in parallel with advanced physics-based model development. This effort outlines how the first stages of qualification can be reduced from the typical 20+-year development cycle to 5 to 7 years by deploying accelerated irradiation testing platforms. As with any accelerated test, these methods are prototypic in some aspects and less so in others; however, by coupling with advanced fuel performance modeling and simulation capabilities, the larger space of irradiation parameters and material response provided offers advantages for the validation of physics-based models supporting the deployment of novel fuel designs. As a test case, this paper utilizes a proposed Mark II fuel system for the upcoming VTR. Thus, an accelerated qualification method can be tested for the development of MARK II driver fuel so that by the time of VTR startup, lead test assemblies for a Mark II fuel can be initiated.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Time-dependent THMC properties and microstructural evolution of damaged rocks in excavation damage zone

Modeling coupled thermo-hydro-mechanical-chemical (THMC) processes in host rocks near high-level nuclear waste (HLW) repositories at various time scales is an extremely challenging task. The current study integrates experimental, theoretical, and numerical methods in assessing the evolution of excavation damage zone (EDZ) over time and its implication on the long-term migration of hazardous species. Argillite and rock salt and are the focus of this study. The first part of the report presents a novel time-dependent directional microcrack damage theory for generic brittle rocks. It features detailed statistical description of the microcracks within a damaged solid, permitting a direct upscaling of microscale processes such as crack growth kinetics, crack closure/opening, sliding friction to explain the macroscopic creep, nonlinear elasticity, shear dilation, and loading-unloading hysteresis. This provides a basic platform for describing the anisotropic mechanical and transport properties of damaged rocks during excavation and subsequent THMC loadings. The model is validated and numerically implemented to Finite Element (FE) package ABAQUS through the user-defined material (UMAT) interface and have demonstrated great potential in resolving the time-dependent and anisotropic evolution of damage in the EDZ. The second part of the report presents a multi-scale experimental effort in characterizing the thermal, hydraulic, and mechanical properties of Mancos shale and Avery Island salt. For the Mancos shale, triaxial compression tests are performed at different confining pressures and temperatures to probe its thermomechanical properties relevant to HLW repositories. The obtained stress-strain data are interpreted using the proposed directional damage theory. Post-test specimens are subjected to gas permeability tests to reveal the correlation between permeability and the degree of microcracking. At microscale, temperature-controlled nanoindentation tests are performed and found a linear correlation between fracture toughness and elastic modulus from 25°C to 300°C. For Avery Island salt, we have designed and manufactured a novel relative-humidity controlled uniaxial creep device. Long-term creep tests at low stresses (< 5 MPa) are performed at different levels of relative humidity (RH). Besides confirming the much higher creep rates as one would expect through extrapolating the high-stress creep data, the results reveal that the steady-state creep rate of rock salt is strongly dependent on the ambient RH, an aspect that is often neglected in the literature. Both behaviors can be attributed to the pressure-solution creep mechanism which dominates at low stress and high RH levels. The third part of the report explores a set of numerical strategies in modeling the THMC behavior of porous geomaterials. A fully implicit, monolithic FE solution that can flexibly interface with different material models and coupling mechanisms for THMC problems is developed and verified through the ABAQUS user-defined element (UEL) interface. The scheme is used to study the THM response of a hypothetical HLW storage site with reference to an existing in-situ heater test. Strategies for integrating the UEL and the microcrack UMAT are suggested. Another numerical endeavor of this study is to implement a higher-order asymptotic homogenization method to account for the heterogeneous porous structures. The same method is then extended to perform microstructure-informed thermo-mechanical modeling of generalized continua. The above outcomes of this project provide a strong thrust towards enhancing the fundamental understanding and modeling capability of the long-term evolution of host rocks in EDZ, thus helping achieve the design goal of 1-million-year isolation of high-level nuclear wastes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Optimization of Conditions for Photoluminescence-Based Sensing of Critical Minerals: Strategies and Outlook

Economically critical minerals and metals are vital to America’s security, with application areas in energy, advanced technologies, and defense systems. The growing implementation of renewable energy sources such as electric vehicles is expected to significantly increase demand for these minerals, while the global supply is monopolistic, with most of the production occurring in a few countries outside of the US. To mitigate potential supply chain vulnerabilities, the domestic production of economically critical metals has become a bipartisan priority of the US government, and unconventional sources such as coal and its utilization byproducts such as fly ash and acid mine drainage are being actively explored as an alternative method for meeting domestic demand. Slow and expensive characterization methods for critical metals present a significant pain point for domestic production, which has led to the exploration of alternative low-cost, portable platforms capable of detecting target metals during resource prospecting and downstream process monitoring. The National Energy Technology Laboratory has developed a portable fiber optic-based luminescence spectrometer that utilizes a metal-organic framework (MOF) material to detect and distinguish parts-per-billion levels of the visible-emitting rare earth elements terbium, dysprosium, samarium, and europium, which are all economically critical metals. Although preliminary results with this system are promising, a crucial barrier to practical deployment is the ability to operate in low pH, high ionic strength environments, as acidic conditions and the presence of other metal ions can significantly reduce luminescence signal. Here, current strategies related to sample treatment, material design, and sensor configuration are discussed in the context of improving sensor performance in application-relevant conditions. Additionally, future opportunities, such as the optimization of the sensing binding environment through computational methods and specific metals to be removed for treatment will be discussed, presenting a forward-looking view for innovation in luminescent sensing of critical metals.

36 MATERIALS SCIENCE↗

MoS 2 Nanoplatelets on Hybrid Core-Shell (HyCoS) AuPd NPs for Hybrid SERS Platform for Detection of R6G

In this work, a novel hybrid SERS platform incorporating hybrid core-shell (HyCoS) AuPd nanoparticles (NPs) and MoS 2 nanoplatelets has been successfully demonstrated for strong surface-enhanced Raman spectroscopy (SERS) enhancement of Rhodamine 6G (R6G). A significantly improved SERS signal of R6G is observed on the hybrid SERS platform by adapting both electromagnetic mechanism (EM) and chemical mechanism (CM) in a single platform. The EM enhancement originates from the unique plasmonic HyCoS AuPd NP template fabricated by the modified droplet epitaxy, which exhibits strong plasmon excitation of hotspots at the nanogaps of metallic NPs and abundant generation of electric fields by localized surface plasmon resonance (LSPR). Superior LSPR results from the coupling of distinctive AuPd core-shell NP and high-density background Au NPs. The CM enhancement is associated with the charge transfer from the MoS 2 nanoplatelets to the R6G. The direct contact via mixing approach with optimal mixing ratio can effectively facilitate the charges transfer to the HOMO and LUMO of R6G, leading to the orders of Raman signal amplification. The enhancement factor (EF) for the proposed hybrid platform reaches ~10 10 for R6G on the hybrid SERS platform.

36 MATERIALS SCIENCE↗

Three-Dimensional Integration of Functional Oxides and Crystalline Silicon for Optical Neuromorphic Computing Using Nanometer-Scale Oxygen Scavenging Barriers

Dating to the first reports of epitaxial oxide deposition on Si(001), the integration of complex oxides on silicon has been a fast-moving area of research, where fundamental materials physics is intimately connected to tremendous technological promise in such areas as integrated electronics, optical neuromorphic and quantum computing, and sensing, to name a few. Despite their great promise, devices relying on the co-integration of silicon and epitaxial perovskites are typically limited to basic, planar geometries due to practical issues with their fabrication. In this paper, we overcome these long-standing challenges by developing a method to produce high-quality Si(001)/TMO/Si(001)/TMO heterostructures without wafer bonding, resulting in the straightforward three-dimensional integration of functional complex oxides and active Si(001) layers into a technologically relevant platform that is needed for on-chip hardware implementations of neuromorphic computing based on optical signals. We present detailed structural and chemical characterization of our heterostructures and discuss generalized design rules for their fabrication. Our results exponentially expand the universe of practically achievable TMO-based integrated devices and push this promising class of materials closer to realizing their full technological potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multimodal In Situ Characterization Uncovers Unexpected Stability of a Cobalt Electrocatalyst for Acidic Sustainable Energy Technologies

An accelerated development of durable and affordable sustainable energy technologies is often hindered by a limited understanding of how non-precious materials within these systems degrade. In acidic proton exchange membrane fuel cells and water electrolyzers, metallic cobalt (Co) is considered an unstable component that is often combined with precious metals or other stabilizers. To understand the mechanisms behind Co instability, we employ an experimental platform that quantifies dissolution with on-line inductively coupled plasma mass spectrometry and product formation with electrochemical mass spectrometry during electrochemical testing, along with ex- situ characterization. Under varied conditions (electrocatalysis, time, gas-type saturation, and ion concentration), windows of Co stability are observed that are different than predicted with classical chemical thermodynamics, suggesting new stabilization and degradation mechanisms than previously understood. Notably, Co is active for the hydrogen evolution reaction (HER), with prolonged stability that is ~300 mV different than thermodynamically projected. Additionally, in an oxygenated environment, Co concurrently performs the HER and oxygen reduction reaction (ORR) yet undergoes different morphology changes and dissolution mechanisms. Interestingly, in the absence of electrocatalysis, there is a 22x decrease in dissolution in an oxygen-free environment, proposing a route to decrease Co losses during device shutdown protocols. Lastly, under more extreme operating conditions, Co becomes stable after a substantial amount of dissolution, suggesting that high concentrations of Co 2+ ions in the microenvironment induce the formation of a stable CoHO 2 surface. Altogether, these results can be leveraged to improve the design and development of more robust and cost-effective sustainable energy technologies, as well as promote strategic strategies for prolonged material utilization.

Dissolution↗

Constructing Self-Labeled Materials Imaging Datasets from Open Access Scientific Journals with EXSCLAIM!

Due to recent improvements in image resolution and acquisition speeds, materials microscopy is experiencing an explosion in imaging data. Yet, despite the volume of images generated, the overall accessibility landscape is highly fragmented, as researchers who do release images to the public, often only do so as snapshots of their larger private dataset in context of scientific journal publications. The effort to automatically consolidate images and descriptive information from web-based platforms has garnered broad attention from the computer vision, language technologies, and chemistry/materials informatics communities. However, these methods are problematic for scientific figures because over 30% of figures are compound in nature, and it is the individual images themselves, paired with relevant context, that are necessary for construction a proper labeled dataset. To this end, we outline in this paper the design of a software pipeline for the automatic EXtraction, Separation, and Caption-based natural Language Annotation of IMages from scientific figures (EXSCLAIM!). Successful consolidation of materials imaging across literature sources will enhance navigation and searchability of materials microscopy images for both novice and experienced researchers, as well as establish the framework necessary for users to search by images, text, or some combination of both.

36 MATERIALS SCIENCE↗

Solvent-Free Manufacturing of Lithium-Ion Battery Electrodes via Cold Plasma

Slurry casting has been used to fabricate lithium-ion battery electrodes for decades, which involves toxic and expensive organic solvents followed by high-cost vacuum drying and electrode calendering. This work presents a new manufacturing method using a nonthermal plasma to create inter-particle binding without using any polymeric binding materials, enabling solvent-free manufacturing electrodes with any electrochemistry of choice. The cold-plasma-coating technique enables fabricating electrodes with thickness (>200 μm), high mass loading (>30 mg cm -2 ), high peel strength, and the ability to print lithium-ion batteries in an arbitrary geometry. This crosscutting, chemistry agnostic, platform technology would increase energy density, eliminate the use of solvents, vacuum drying, and calendering processes during production, and reduce manufacturing cost for current and future cell designs. Here, lithium iron phosphate and lithium cobalt oxide were used as examples to demonstrate the efficacy of the cold-plasma-coating technique. It is found that the mechanical peel strength of cold-plasma-coating-manufactured lithium iron phosphate is over an order of magnitude higher than that of slurry-casted lithium iron phosphate electrodes. Full cells assembled with a graphite anode and the cold-plasma-coating-lithium iron phosphate cathode offer highly reversible cycling performance with a capacity retention of 81.6% over 500 cycles. For the highly conductive cathode material lithium cobalt oxide, an areal capacity of 4.2 mAh cm -2 at 0.2 C is attained. We anticipate that this new, highly scalable manufacturing technique will redefine global lithium-ion battery manufacturing providing significantly reduced plant footprints and material costs.

25 ENERGY STORAGE↗

Preserving the Josephson Coupling of Twisted Cuprate Junctions via Tailored Silicon Nitride Circuits Boards

Controlled fabrication of twisted van der Waals heterostructures is essential to unlock the full potential of moiré materials. However, achieving reproducibility remains a major challenge, particularly for air-sensitive materials such as Bi 2 Sr 2 CaCu 2 O 8 + δ (BSCCO), where it is crucial to preserve the intrinsic and delicate superconducting properties of the interface throughout the entire fabrication process. Here, a dry, inert and cryogenic assembly method is presented that combines silicon nitride nanomembranes (NMBs) with pre-patterned electrodes and the cryogenic stacking technique (CST) to fabricate high-quality twisted BSCCO Josephson junctions (JJs). This protocol prevents thermal and chemical degradation during both interface formation and electrical contact integration. It is also found that asymmetric membrane designs, such as a double cantilever, effectively suppress vibration-induced disorder due to wire bonding, resulting in sharp and hysteretic current–voltage characteristics. The junctions exhibit a twist-angle-dependent Josephson coupling with magnitudes comparable to the highest-performing devices reported to date, but achieved through a straightforward and versatile contact method, offering a scalable and adaptable platform for future applications. These findings highlight the importance of both interface and contact engineering in addressing reproducibility in superconducting van der Waals heterostructures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Co-Design of Charge Transport Superhighways to Connect Catalytic Sites in Soft Photoelectrochemical Systems

Efficient photon-to-electron-to-molecule conversion requires multi-length scale control over charge transport pathways, where electronic charges are delivered to catalytic sites under high mass transport flux. A fundamental question is how can we co-design charge transport pathways to promote efficient charge transfer to/from catalytic sites in complex three-dimensional architectures? Soft conducting polymer systems offer exceptional promise to provide three-dimensional charge transport networks, where electrolyte (ion and solvent) can interdiffuse to promote long-lived charge carriers and the molecular nature allows for strategic synthetic design of catalytic sites. Herein we combine theoretical and experimental approaches to investigate the earliest stages of photoelectrochemical deposition of near-surface catalytic sites (Pt) on soft bulk heterojunction polymeric semiconductors composed of a prototype donor (PTB7-Th) and a prototype acceptor (N2200) as a model system towards better understanding molecular catalyst-polymer site interactions. We focus initially on photoelectrochemical deposition of low Pt loadings, nanoparticle sizes (formed by progressive nucleation) below 20 nm, for both density functional theory (DFT) modeling studies and for spectroscopic characterization using surface-sensitive X-ray and UV-photoemission (XPS/UPS). DFT modeling of “n-type” N2200 slabs reveal for the first time that sulfur atoms in the thiophene units serve as the lowest-energy adsorption sites for single Pt atoms, while larger Pt clusters engage more complexly with both thiophene and naphthalene diimide (NDI) core sites. Changes in chemical composition observed by X-ray photoelectron spectroscopy (XPS) support the DFT predictions, and the angle-resolved measurements reveal that Pt nucleation initiates at subsurface sites which appear to be localized active domains that promote charge transport/transfer and enable vertical growth toward the surface. These results suggest that light-activated Pt nanoparticle deposition decorates energetically distinct sites, where photoactivity is dictated by the local energetics of those sites, and the fact that they represent the termini of charge transport “super-highways” – a small percentage of the total volume of the donor/acceptor polymeric active layer which carries most of the photocurrent generated during both Pt deposition and photoelectrochemical HER. We posit that these initial studies provide a foundational strategy for design of catalytic sites in the near surface regions of complex polymeric materials and advancing soft semiconductor-based photoelectrochemical systems. Achieving a nanometer-scale understanding of catalyst deposition and the impact of local composition and energetics on that placement, should ultimately provide the design guidelines (co-design) for a broad array of catalysts at sites that optimize that efficiency and maximize platform durability.

14 SOLAR ENERGY↗

Topological Hall effect in magnetic topological insulator films

Geometric Berry phase can be induced either by spin–orbit coupling, giving rise to the anomalous Hall effect in ferromagnetic materials, or by chiral spin texture, such as skyrmions, leading to the topological Hall effect. Recent experiments have revealed that both phenomena can occur in topological insulator films with magnetic doping, thus providing us with an intriguing platform to study the interplay between these two phenomena. In this work, we report on a numerical simulation of the anomalous Hall and topological Hall effects in a four-band model that can properly describe the quantum well states in the magnetic topological insulator films by combining Landauer–Büttiker formula and the iterative Green’s function method. Our numerical results suggest that spin–orbit coupling in this model plays a different role in the quantum transport in the clean and disordered limits. In the clean limit, spin–orbit coupling mainly influences the longitudinal transport but does not have much effect on topological Hall conductance. In the disordered limit, the longitudinal transport is determined by disorder scattering and spin–orbit coupling is found to affect strongly the topological Hall conductance. Here, this sharp contrast unveils a dramatic interplay between spin–orbit coupling and disorder effect in topological Hall effect in magnetic topological insulator systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Precise Modulation of CO 2 Sorption in Ti 8 Ce 2 –Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility

Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti 8 Ce 2 -oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti 8 Ce 2 -BA (BA denotes benzoic acid) manifests a distinctive two-step profile during CO 2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in-situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between CO 2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. Furthermore, these insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Three-dimensional topological magnetic monopoles and their interactions in a ferromagnetic meta-lattice

Topological magnetic monopoles (TMMs), also known as hedgehogs or Bloch points, are three-dimensional (3D) nonlocal spin textures that are robust to thermal and quantum fluctuations due to the topology protection. Although TMMs have been observed in skyrmion lattices, spinor Bose–Einstein condensates, chiral magnets, vortex rings and vortex cores, it has been difficult to directly measure the 3D magnetization vector field of TMMs and probe their interactions at the nanoscale. Here, we report the creation of 138 stable TMMs at the specific sites of a ferromagnetic meta-lattice at room temperature. We further develop soft x-ray vector ptycho-tomography to determine the magnetization vector and emergent magnetic field of the TMMs with a 3D spatial resolution of 10 nm. This spatial resolution is comparable to the magnetic exchange length of transition metals, enabling us to probe monopole-monopole interactions. We find that the TMM and anti-TMM pairs are separated by 18.3±1.6 nm, while the TMM and TMM, anti-TMM and anti-TMM pairs are stabilized at comparatively longer distances of 36.1±2.4 nm and 43.1±2.0 nm, respectively. We also observe virtual TMMs created by magnetic voids in the meta-lattice. This work demonstrates that ferromagnetic meta lattices could be used as a platform to create and investigate the interactions and dynamics of TMMs. Furthermore, we expect that soft x-ray vector ptycho-tomography can be broadly applied to quantitatively image 3D vector fields in magnetic and anisotropic materials at the nanoscale.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Co-Optimization of Boost Converter Reliability and Volumetric Power Density [Brief]

Optimized designs were achieved using a genetic algorithm to evaluate multi-objective trade space, including Mean-Time-Between-Failure (MTBF) and volumetric power density. This work provides a foundational platform that can be used to optimize additional power converters, such as an inverter for the EV traction drive system as well as trade-offs in thermal management due to the use of different device substrate materials.

33 ADVANCED PROPULSION SYSTEMS↗

Data Based Shock Test Specification

It is vital that avionic packages used for testing and certifying the reliability and safety of U.S. nuclear weapons with platform aircraft survive exposure to shock environments during transportation and delivery. The objective of this research was to characterize the response to these transportation shock environments delivering accurate shock test specifications in order to set laboratory programming material and device certification rigor. Responses to shock events were analyzed in the frequency domain via the Shock Response Spectrum (SRS). Shocks were then grouped based on respective behavior of maximum response accelerations which were pseudorandomly resampled and compared to test data to form test specifications based on the MinerPalmgren hypothesis. In addition to discovering significant over testing in current shock specifications, a new systematic, data-driven approach to designing shock specifications was formulated.

42 ENGINEERING↗

ESSENCE- A rapid, shear-enhanced, flow-through, capacitive electrochemical platform for rapid detection of biomolecules

The rapid, sensitive, and selective detection of target analytes using electrochemical sensors are challenging. ESSENCE, a new Electrochemical Sensor that uses a Shear-Enhanced, flowthrough Nanoporous Capacitive Electrode, overcomes current electrochemical sensors' response limitations, selectivity, and sensitivity limitations. ESSENCE is a microfluidic channel packed with transducer material sandwiched by a top and bottom microelectrode. The room-temperature instrument less integration process allows the switch of the transducer materials to make up the porous electrode without modifying the electrode architecture or device protocol. ESSENCE can be used to detect both biomolecules and small molecules by simply changing the packed transducer material. Electron microscopy results confirm the high porosity. In conjunction with the non-planar interdigitated electrode, the packed transducer material results in a flow-through porous electrode. Electron microscopy results confirm the high porosity. The enhanced shear forces and increased convective fluxes disrupt the electric double layer's (EDL) diffusive process in ESSENCE. This disruption migrates the EDL to high MHz frequency allowing the capture signal to be measured at around 100 kHz, significantly improving device timing (rapid detection) with a low signal-to-noise ratio. The device’s unique architecture allows us multiple configuration modes for measuring the impedance signal. This allows us to use highly conductive materials like carbon nanotubes. We show that by combining single-walled carbon nanotubes as transducer material with appropriate capture probes, NP-µIDE has high selectivity and sensitivity for DNA (fM sensitivity, selective against non-target DNA), breast cancer biomarker proteins (p53, pg/L sensitivity, selective against non-target HER2).

Cheng, Yu-Hsuan↗

Solar cell contacts: quantifying the impact of interfacial layers on selectivity, recombination, charge transfer, and V oc

Interfacial layers (IFLs) are ubiquitous in solar cells, but their precise impact on carrier transfer rates and the relation of these rates to performance metrics and the concepts of selectivity and recombination is lacking. We report the use of a well-defined interdigitated back-contact (IBC) silicon solar cell to determine the precise role of such IFLs. We characterize the action of the common IFL spiro-OMeTAD by making it a third contact to the IBC cell. This architecture creates three solar cells within a single structure that, with numerical simulation, provide the exchange current densities (i.e., charge transfer rates) for electrons ( J 0n ) and holes ( J 0p ) and the quasi Fermi-level splitting in the absorber, which measures the balance of generation and recombination. Further, we describe the relation of V oc to contact recombination, the asymmetry in electron/hole collection rates at a single contact (contact selectivity), and the asymmetry in collection rates of the same carrier at separate contacts (carrier selectivity). Relative to bare gold, neat spiro-OMeTAD reduces J 0n and J 0p (their geometric mean ( J 0n J 0p ) 0.5 decreases by 10 4 ), decreasing contact recombination. Addition of the common dopant Li-TFSI and air increase J 0p / J 0n by 10 6 with little effect on ( J 0n J 0p ) 0.5 , increasing contact hole selectivity. The significant increase in V oc observed by introducing spiro-OMeTAD/Li-TFSI IFLs into the cells studied, however, is due to an increase in the carrier selectivity rather than the contact selectivity or recombination of the spiro-OMeTAD-modified contact. Operando measurements further show voltage-dependent changes in the J 0 s, demonstrating that spiro-OMeTAD contributes to hysteresis. Broader context : Solar cells operate by photogenerating excess charge carriers in an absorber material and, in competition with recombination, asymmetrically extracting them at so-called carrier-selective contacts, one that ideally collects only electrons and the other, only holes. Particularly in emerging photovoltaics such as perovskites, thin layers of organic semiconductors or related materials are introduced between the absorber and contact to improve power conversion efficiency. In terms of interfacial charge transfer, a prevailing view is that such interfacial layers improve performance by helping block the collection of the undesired carrier, considered a form of recombination. We use a novel platform to study the simultaneous impact of spiro-OMeTAD, a common interfacial layer, on the collection of electrons, the collection of holes, and on the recombination of electrons and holes. We quantitatively demonstrate that spiro-OMeTAD layers indeed passivate the contact toward recombination, but that larger improvements in the open-circuit voltage, a key cell metric, can come not only from this but also from increasing the asymmetry of the collection of electrons in the system. Further, operando measurements show transient changes in the properties of spiro-OMeTAD which suggest that it contributes to hysteresis phenomena commonly observed in perovskite and other solar cells.

36 MATERIALS SCIENCE↗