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At least 613 records · Page 34

Regiospecific N -alkyl substitution tunes the molecular packing of high-performance non-fullerene acceptors

The rapid development of non-fullerene acceptors (NFAs) with strong near-infrared absorption has led to remarkably enhanced short-circuit current density (J sc ) values in organic solar cells (OSCs). NFAs based on the benzotriazole (Bz) fused-ring π-core have great potential in delivering both high J sc and decent open-circuit voltage values due to their strong intramolecular charge transfer with reasonably low energy loss. Here in this work, we have designed and synthesized a series of Bz-based NFAs, PN6SBO-4F, AN6SBO-4F and EHN6SEH-4F, via regiospecific N-alkyl engineering based on the high-performance NFA mBzS-4F that was reported previously. The molecular packing of mBzS-4F, AN6SBO-4F, and EHN6SEH-4F single crystals was analyzed using X-ray crystallography in order to provide a comprehensive understanding of the correlation between the molecular structure, the charge-transporting properties, and the solar cell performance. Compared with the typical honeycomb single-crystal structure of Y6 derivatives, these NFAs exhibit distinctly different molecular packing patterns. The strong interactions of terminal indanone groups in mBzS-4F and the J-aggregate-like packing in EHN6SEH-4F lead to the formation of ordered 3D networks in single-crystals with channels for efficient charge transport. Consequently, OSCs based on mBzS-4F and EHN6SEH-4F show efficient photon-to-current conversions, achieving the highest power conversion efficiency of 17.48% with a Jsc of 28.83 mA cm -2 .

36 MATERIALS SCIENCE↗

Relaxed Current Matching Requirements in Highly Luminescent Perovskite Tandem Solar Cells and Their Fundamental Efficiency Limits

Perovskite-based tandem solar cells are of increasing interest as they approach commercialization. Here we use experimental parameters from optical spectroscopy measurements to calculate the limiting efficiency of perovskite–silicon and all-perovskite two-terminal tandems, employing currently available bandgap materials, as 42.0% and 40.8%, respectively. We show luminescence coupling between subcells (the optical transfer of photons from the high-bandgap to low-bandgap subcell) relaxes current matching when the high-bandgap subcell is a luminescent perovskite. We calculate that luminescence coupling becomes important at charge trapping rates (=10 6 s -1 ) already being achieved in relevant halide perovskites. Luminescence coupling increases flexibility in subcell thicknesses and tolerance to different spectral conditions. For maximal benefit, the high-bandgap subcell should have the higher short-circuit current under average spectral conditions. This can be achieved by reducing the bandgap of the high-bandgap subcell, allowing wider, unstable bandgap compositions to be avoided. Lastly, we visualize luminescence coupling in an all-perovskite tandem through cross-section luminescence imaging.

14 SOLAR ENERGY↗

Growth and characterization of high-quality Zr doped AlN epilayers

AlN stands out for its remarkable figures of merit for electronic and photonic devices, attributed to its ultrawide bandgap of ∼6.1 eV and an exceptionally high critical field of ∼15 MV/cm. More recently, zirconium (Zr) doped AlN (AlN:Zr) has also been identified as a promising material platform for the exploration of solid-state qubits for quantum information and technology, high performance piezoelectric acoustic wave resonators, and optically triggered ultrafast power switching devices facilitated by optically activating Zr related impurities. Despite the significant potential, the ability for producing AlN:Zr epitaxial structures has yet to be established. In this study, we have achieved AlN:Zr epilayers with a high Zr doping level [NZr] of up to 1020 cm−3 using industrial standard metal-organic chemical vapor deposition growth technique. High crystalline quality of AlN:Zr was confirmed by x-ray diffraction, revealing a narrow full width at half maximum of the (002) rocking curve at 216 arcsec for 1.8 μm thick epilayers deposited on sapphire at [NZr]=1020 cm−3. Zr doping was observed to slightly increase the c-lattice constant to 4.992 Å for AlN:Zr (at [NZr]=1020 cm−3) compared to 4.980 Å for undoped AlN. X-ray photoelectron spectroscopy measurement results verified the substitution of Zr at the Al site (ZrAl). The formation of (ZrAl–VN) complexes, which are predicted to possess all the desired properties required by quantum qubits, was confirmed through optical absorption studies. The realization of high-quality AlN:Zr epilayers significantly broadens the scope of technologically significant device applications for AlN.

36 MATERIALS SCIENCE↗

Near-zero-index ultra-fast pulse characterization

Transparent conducting oxides exhibit giant optical nonlinearities in the near-infrared window where their linear index approaches zero. Despite the magnitude and speed of these nonlinearities, a “killer” optical application for these compounds has yet to be found. Because of the absorptive nature of the typically used intraband transitions, out-of-plane configurations with short optical paths should be considered. In this direction, we propose an alternative frequency-resolved optical gating scheme for the characterization of ultra-fast optical pulses that exploits near-zero-index aluminium zinc oxide thin films. Besides the technological advantages in terms of manufacturability and cost, our system outperforms commercial modules in key metrics, such as operational bandwidth, sensitivity, and robustness. The performance enhancement comes with the additional benefit of simultaneous self-phase-matched second and third harmonic generation. Because of the fundamental importance of novel methodologies to characterise ultra-fast events, our solution could be of fundamental use for numerous research labs and industries.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Direct Observation of the ππ* to nπ* Transition in 2-Thiouracil via Time-Resolved NEXAFS Spectroscopy

The photophysics of nucleobases has been the subject of both theoretical and experimental studies over the past decades due to the challenges posed by resolving the steps of their radiationless relaxation dynamics, which cannot be described in the framework of the Born–Oppenheimer approximation (BOA). In this context, the ultrafast dynamics of 2-thiouracil has been investigated with a time-resolved NEXAFS study at the Free Electron Laser FLASH. Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS) can be used to observe electronic transitions in ultrafast molecular relaxation. We performed time-resolved UV-pump/X-ray probe absorption measurements at the sulfur 2s (L1) and 2p (L2/3) edges. We are able to identify absorption features corresponding to the S2 (ππ*) and S1 (nπ*) electronic states. We observe a delay of 102 ± 11 fs in the population of the nπ* state with respect to the initial optical excitation and interpret the delay as the time scale for the S2 → S1 internal conversion. We furthermore identify oscillations in the absorption signal that match a similar observation in our previous X-ray photoelectron spectroscopy study on the same molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tracking carrier and exciton dynamics in mixed-cation lead mixed-halide perovskite thin films

Mixed-cation lead mixed-halide perovskites simultaneously possess structural stability and high power conversion efficiency. A thorough study of both carrier and exciton dynamics is needed to understand the photophysical properties that underpin its superior photovoltaic performance. By utilizing a broadband transient absorption spectroscopy, we observe the carrier and exciton dynamics in a FA 0.85 Cs 0.15 Pb(I 0.97 Br 0.03 ) 3 (FCPIB) perovskite by simultaneously resolving the carrier and exciton contribution to the transient change of the absorption spectra, from which the carrier density and exciton oscillator strength can be determined. Our data reveal a quick and significant conversion of the photogenerated carriers to excitons, on top of the usual carrier recombination process. Moreover, the decay of carrier density shows a change of kinetics from a second-order recombination at high pump fluence to a third-order recombination at low pump fluence. Our analysis utilizes band anharmonicity, presents an independent determination of electronic temperature and quasi-Fermi energy, and reveals an interesting interplay among the processes of carrier cooling, exciton formation/decay and carrier recombination, all as a function of time after photoexcitation. Our work demonstrates the use of pump fluence as a knob to tune the relative populations of carriers and excitons in halide perovskite materials.

36 MATERIALS SCIENCE↗

Local electric field measurement in GaN diodes by exciton Franz–Keldysh photocurrent spectroscopy

The eXciton Franz–Keldysh (XFK) effect is observed in GaN p–n junction diodes via the spectral variation of photocurrent responsivity data that redshift and broaden with increasing reverse bias. Photocurrent spectra are quantitatively fit over a broad photon energy range to an XFK model using only a single fit parameter that determines the line shape and the local bias (V l ), uniquely determining the local electric field maximum and depletion widths. As expected, the spectrally determined values of V l vary linearly with the applied bias (V) and reveal a large reduction in the local electric field due to electrostatic non-uniformity. The built-in bias (V bi ) is estimated by extrapolating V l at V=0, which, when compared with independent C-V measurements, indicates an overall ±0.31 V accuracy of V l . This demonstrates sub-bandgap photocurrent spectroscopy as a local probe of electric field in wide bandgap diodes that can be used to map out regions of device breakdown (hot spots) for improving electrostatic design of high-voltage devices.

42 ENGINEERING↗

Solid-to-plasma transition of polystyrene induced by a nanosecond laser pulse within the context of inertial confinement fusion

Laser Direct Drive (LDD) Inertial Confinement Fusion (ICF) involves irradiating a spherical target of thermonuclear fuel coated with an ablator, usually made of polystyrene. Laser energy absorption near the target surface leads to matter ablation, hydrodynamic shocks, and ultimately capsule implosion. The conservation of spherical symmetry is crucial for implosion efficiency, yet spatial modulations in laser intensity can induce nonuniformities, causing the laser imprint phenomenon. Understanding laser imprint, especially considering the initial solid state, is essential for advancing LDD ICF. A first microscopic model of solid-to-plasma transition was built in 2019, accounting for laser absorption in the solid state with a band structure based ionization model. This model has been improved to include chemical fragmentation and a more accurate description of electron collision frequency in various matter states. The latest development involves assessing the model reliability by comparing theoretical predictions with experimental observations. Despite the success of this approach, questions remain, leading to further investigations and observations under different irradiation conditions. This work presents an experiment with a nanosecond pulse, taking into account hydrodynamic effects, and measures transmission dynamics over the entire laser beam area to observe two-dimensional effects. As a result, the objective is to adapt the theoretical model, couple it with a hydrodynamic code, and observe additional effects related to the initial solid state.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Amplified Spontaneous Emission from Electron–Hole Quantum Droplets in Colloidal CdSe Nanoplatelets

Two-dimensional cadmium selenide nanoplatelets (NPLs) exhibit large absorption cross sections and homogeneously broadened band-edge transitions that offer utility in wide-ranging optoelectronic applications. Here, we examine the temperature-dependence of amplified spontaneous emission (ASE) in 4- and 5-monolayer thick NPLs and show that the threshold for close-packed (neat) films decreases with decreasing temperature by a factor of 2-10 relative to ambient temperature owing to extrinsic (trapping) and intrinsic (phonon-derived line width) factors. Interestingly, for pump intensities that exceed the ASE threshold, we find development of intense emission to lower energy in particular provided that the film temperature is <= 200 K. For NPLs diluted in an inert polymer, both biexcitonic ASE and low-energy emission are suppressed, suggesting that described neat-film observables rely upon high chromophore density and rapid, collective processes. Transient emission spectra reveal ultrafast red-shifting with the time of the lower energy emission. Taken together, these findings indicate a previously unreported process of amplified stimulated emission from polyexciton states that is consistent with quantum droplets and constitutes a form of exciton condensate. For studied samples, quantum droplets form provided that roughly 17 meV or less of thermal energy is available, which we hypothesize relates to polyexciton binding energy. Polyexciton ASE can produce pump-fluence-tunable red-shifted ASE even 120 meV lower in energy than biexciton ASE. Finally, our findings convey the importance of biexciton and polyexciton populations in nanoplatelets and show that quantum droplets can exhibit light amplification at significantly lower photon energies than biexcitonic ASE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Electrochemical Sulfur-Based Phase Evolution via Complementary Insight from Operando Spatially Resolved X-ray Diffraction and X-ray Absorption Spectroscopy

Lithium/sulfur batteries are emerging as promising candidates for use in large-scale energy storage, but practical challenges, including insufficient power density and polysulfide shuttling, remain. Here, this work presents the first use of operando energy dispersive X-ray diffraction (EDXRD) to monitor Li/S electrochemistry within a liquid electrolyte. Complementary operando synchrotron-based EDXRD, X-ray absorption spectroscopy (XAS), X-ray powder diffraction (XPD), and ex situ laboratory Raman analysis provide evidence for α-S 8 conversion upon discharge into Li 2 S x polysulfide phases and conversion into β-S 8 during charge. Understanding the underlying mechanisms of sulfur reduction and oxidation within thick electrodes will enable advances in next-generation Li/S batteries and material design.

36 MATERIALS SCIENCE↗

Single-atom molybdenum doping induces nickel oxide-to-hydroxide transformation for enhanced alkaline hydrogen evolution

NiMoO x compounds are widely regarded as among the most efficient non-noble metal catalysts for the hydrogen evolution reaction (HER). Nevertheless, understanding the structural evolution under in situ conditions and further enhancing their performance remain key challenges. Herein, we report that single-atom Mo doping in NiO significantly enhances its HER activity, reducing the overpotential to 131 mV at 10 mA cm −2 compared to undoped NiO. In situ X-ray absorption spectroscopy and Raman spectroscopy reveal that under catalytic conditions, Mo single atoms remain structurally stable, while Ni 2+ species in NiO are converted to Ni(OH) 2 in alkaline media under the applied working potential for HER. Notably, this transformation is absent in undoped NiO, indicating that Mo doping promotes the formation of active Ni(OH) 2 sites, which, in turn, accelerate the rate-limiting water dissociation step. These findings provide critical mechanistic insights into the structural evolution of NiMoO x during alkaline HER and highlight the importance of in situ studies in the development of highly efficient catalysts.

58 GEOSCIENCES↗

Chapter 14: Surface plasmon resonance enhanced artificial photosynthesis of chemical fuels for energy storage

Nanostructured noble metals such as Au, Ag, and Cu have interesting optical properties because of the oscillation motions of their surface electrons upon strong coupling with light under resonance conditions. This resonant oscillation motion of conduction electrons refers to surface plasmon resonance (SPR) and localized SPR (LSPR) when localized near the surface of a nanoparticle. The extinction spectrum of a solution of plasmonic nanoparticles has tunable wavelength responses from UV to NIR due to strong light scattering and absorption which are highly sensitive to the permittivity of the nanoparticles, their sizes and shapes, and chemical environment. Strong light scattering due to the LSPR of plasmonic nanoparticles creates a strong localized and far-field intensity capable of enhancing light absorption characteristics of a chromophore near a plasmonic surface. Engineering the chromophores’ radiative decay dynamics can be done by 1) increasing its radiative decay rate to increase its photoluminescence intensity and 2) increasing its nonradiative decay rates associated to direct charge transfer to the metal surface. Such interesting photophysical properties of a chromophore can be extended to other light-absorbing materials such as semiconductor thin films and nanostructures. This plasmonic effect on the photophysics of a light-absorbing material can be theoretically and experimentally validated. The phenomenon has also been applied to advanced optoelectronic devices such as organic light-emitting diodes (OLED)1 and organic photovoltaics (OPV).2-4 The local field created by the SPR can provide an intense EM field to enhance photoluminescence emission of an organic chromophore5-8 and Raman scattering of an organic molecule, and single-molecule Raman9-10 can be detected on specially designed LSPR substrate. (Figure 1 on SPR for energy) Recent studies suggest that LSPR can be incorporated in light-harvesting and conversion systems to increase energy conversion in a solar cell and photoelectrochemical cell and chemical transformations of CO2 to chemical fuels.11-12 Plasmonic active metals naturally exhibit catalytic activities for electrochemical fuel conversion that can be enhanced by engineering their structures to form unique catalytic structures such as symmetry-broken Au-Cu Janus nanocrystals.13 These studies are critical to addressing the global challenges of energy14-15 and CO2 emission from nonrenewable sources such as coal, petroleum, and natural gas.16-17 Electrochemical systems comprised of unique photonic structures and functions that enable efficient and affordable energy harvesting/conversion/storage are highly desired for providing safe and environment-friendly energy sources. This chapter reviews our recent work of LSPR enabled photoelectrochemical water splitting and recent advances in LSPR-enabled CO2 reduction and photochemical reactions reported in the literature. Scientific and technical challenges of applying LSPR to enhance these energy conversion and storage systems are discussed at the conclusion of this chapter.

Pan, Shanlin↗

Pursuing Heteroleptic Ligand Design Principles for Photoactive Fe Complexes with Ultrafast X-ray Emission and Variable-Temperature Optical Spectroscopies

Understanding the key parameters that govern the photophysical and photochemical properties of transition metal complexes is essential for the development of efficient photosensitizers for photocatalytic applications. Achieving this objective necessitates clear and detailed investigations of their electronic excited states, for which time-resolved metal Kβ X-ray emission spectroscopy (XES) has proven highly effective. Here, we present a time-resolved Fe Kβ XES study of a heteroleptic Fe(II) polypyridyl carbene complex, [Fe(phen) 2 (C 4 H 10 N 4 )] 2+ (1; phen = 1,10-phenanthroline), utilizing both the valence-to-core and Kβ mainline spectral regions, complemented by variable-temperature transient optical absorption (VT-TA) spectroscopy. Detailed analysis of the time-resolved Kβ XES data, supported by density functional theory (DFT) calculations and an Eyring analysis of the VT-TA data, reveals parallel excited state relaxation dynamics that support an assignment of the long-lived excited state to a triplet metal-centered state. Placing these results in the context of prior studies of heteroleptic Fe(II) polypyridyl cyanide complexes motivated a series of DFT calculations to investigate the effects of ligand structural flexibility and arrangement. These calculations reinforce the experimentally derived conclusion that constraining structural flexibility with multidentate ligands significantly impacts the excited state relaxation dynamics. Furthermore, our study emphasizes that the arrangement of strong field ligands in heteroleptic complexes substantially affects the energy of Jahn–Teller active triplet metal-centered states in low-spin d 6 metal complexes. Together, these findings provide synthetic design principles for extending metal-to-ligand charge transfer excited state lifetimes of heteroleptic Fe complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectral phase singularity and topological behavior in perfect absorption

Perfect absorbers, which can achieve total absorption of all incoming energy, have been extensively studied in the last decades for various important technologies in general wave systems. Here, we show that perfect absorption (PA) is generically associated with topological spectral phase singularity (SPS), carrying conserved and tunable quantized topological invariants in spectral space. The order of topological invariant $\tilde{v}$ depends on the number of degenerate outgoing channels. Two commonly studied absorbers, mirror-backed and all-dielectric structures, are reexamined from a topological perspective to reveal the generation, evolution, and annihilation of SPSs with $\tilde{v}$ = ±1 or even high orders (i.e., $\tilde{v}$ = ±2,±4). A strategy based on charge conservation of SPSs to design dual-band perfect absorbers has been established. Our findings establish the topological origin of the robust existence of PA. More broadly, in this letter, we highlight topology as the fundamental property of conventional scattering behaviors. Finally, this insight could lead to opportunities in applications such as biosensing, topological metasurfaces, and micro/nano thermal radiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A variable X-ray chopper system for phase-sensitive detection in synchrotron X-ray scanning tunneling microscopy

An ultra-high-vacuum compatible X-ray chopper system has been designed, constructed and integrated into the XTIP beamline at the Advanced Photon Source at Argonne National Laboratory. The XTIP beamline can operate at soft X-ray energies from 400 eV to 1900 eV while providing a focused beam down to about 10 µm × 10 µm into the synchrotron X-ray scanning tunneling microscopy (SX-STM) endstation instrument. The X-ray chopper is a critical component for separating topographic information from chemical information in SX-STM through phase-sensitive current detection. Depending on the experimental needs, the modulation frequency can be controlled from 100 Hz to 10 kHz. In addition, the chopper system is fully bakeable and can achieve a base pressure of 10 -10 mbar. Facilities for active water cooling have been designed, but passive cooling through copper braids has been shown to be sufficient at standard chopping frequencies. Using an Fe/Al 2 O 3 /CoAl(111) sample, the separation of the SX-STM current into a chemical component and a stable feedback signal is demonstrated.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Photoionization of seeded combustion products as a method of enhancing the efficiency of magnetohydrodynamic power generators

Here, in this study, we performed an experimental and computational investigation into the feasibility of utilizing photoionization to enhance the electrical conductivity of seeded oxy-fuel combustion products and improve the performance of magnetohydrodynamic (MHD) power generators. We applied a variety of optical and microwave diagnostics to study the ionization and recombination processes of potassium excited by an excimer laser in a high-velocity oxy-fuel free jet. Computational fluid dynamic (CFD) simulations were performed to model the thermophysical properties and species densities of the free jet. The CFD results were validated with position-dependent potassium concentration measurements. Electron recombination exponential lifetimes were measured through time-resolved microwave transmission. The experimental electron lifetimes were compared with lifetimes calculated from CFD-predicted species densities and literature recombination rates. It was determined that K + or O 2 are the most likely recombination partners for photoionized electrons. Time-resolved fluorescence measurements provided evidence of an ionization pathway involving a two-photon ionization of KOH . Finally, a zero-dimensional chemical kinetic model was developed to assess the fundamental viability of inducing a non-equilibrium electron population to provide a net energy return in combustion-driven MHD power generators. We determined that a high energy return is feasible for targeting electrode boundary layers with ultraviolet photoionization. We also found that photoionization could potentially lower the required temperature of the bulk gas flow.

20 FOSSIL-FUELED POWER PLANTS↗

Role of Lithium Codoping in Enhancing the Scintillation Yield of Aluminate Garnets

The aim of this work is to clarify the scintillation-yield enhancement in Lu YAG : Pr scintillators obtained by Li codoping via integrated study of the valence state of activators, the preferential site occupancy of Li codopants, and defect structures from experimental and theoretical insights. Here, with Li codoping, the light yield and energy resolution of 10 × 10 × 10 mm 3 Lu YAG : Pr samples are improved from 156000 to 248000 photons/MeV, and 5.3 to 4.3% at 662 keV,respectively.The optical absorption spectra indicate that Li codoping does not induce conversion of stable Pr 3 + to Pr 4 + in Lu YAG : Pr single crystals. Based on the formation energies of substitutional and interstitial Li sites using density-functional-theory (DFT) calculations and the 7 Li nuclear magnetic resonance results, it is shown that the Li ions prefer to dominantly occupy the fourfold coordinated interstitial sites and fourfold coordinated Al sites. The systematic analysis of thermoluminescence glow curves, positron annihilation lifetime spectroscopies, and defect formation energies derived from DFT calculations reveals that the concentration of isolated Lu and Al vacancies as dominant acceptor defects is reduced by Li codoping, whilst the shallow Li i interstitial defects and the deep V O oxygen vacancies are introduced simultaneously. We propose that the lowering of hole trapping at defects resulting from Li codoping contributes to the scintillation-yield enhancement.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Light-field control of real and virtual charge carriers

We report light-driven electronic excitation is a cornerstone for energy and information transfer. In the interaction of intense and ultrafast light fields with solids, electrons may be excited irreversibly, or transiently during illumination only. As the transient electron population cannot be observed after the light pulse is gone, it is referred to as virtual, whereas the population that remains excited is called real. Virtual charge carriers have recently been associated with high-harmonic generation and transient absorption, but photocurrent generation may stem from real as well as virtual charge carriers. However, a link between the generation of the carrier types and their importance for observables of technological relevance is missing. Here we show that real and virtual charge carriers can be excited and disentangled in the optical generation of currents in a gold–graphene–gold heterostructure using few-cycle laser pulses. Depending on the waveform used for photoexcitation, real carriers receive net momentum and propagate to the gold electrodes, whereas virtual carriers generate a polarization response read out at the gold–graphene interfaces. On the basis of these insights, we further demonstrate a proof of concept of a logic gate for future lightwave electronics. Our results offer a direct means to monitor and excite real and virtual charge carriers. Individual control over each type of carrier will markedly increase the integrated-circuit design space and bring petahertz signal processing closer to reality.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗