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At least 685 records · Page 38

Dynamics of Back Electron Transfer in Dye-Sensitized Solar Cells Featuring 4-tert-Butyl-Pyridine and Atomic-Layer-Deposition Alumina as Surface Modifiers.

A series of dye-sensitized solar cells (DSCs) was constructed with TiO2 nanoparticles and N719 dye. The standard I-3(-)/I- redox shuttle and the Co(1,10-phenanthroline)(3)(3+/2+) shuttle were employed. DSCs were modified with atomic-layered-deposited (ALD) coatings of Al2O3 and/or with the surface-adsorbing additive 4-tert-butyl-pyridine. Current-voltage data were collected to ascertain the influence of each modification upon the back electron transfer (ET) dynamics of the DSCs. The primary effect of the additives alone or in tandem is to increase the open-circuit voltage. A second is to alter the short-circuit current density, J(SC). With dependence on the specifics of the system examined, any of a myriad of dynamics-related effects were observed to come into play, in both favorable (efficiency boosting) and unfavorable (efficiency damaging) ways. These effects include modulation of (a) charge-injection yields, (b) rates of interception of injected electrons by redox shuttles, and (c) rates of recombination of injected electrons with holes on surface-bound dyes. In turn, these influence charge-collection lengths, charge-collection yields, and onset potentials for undesired dark current. The microscopic origins of the effects appear to be related mainly to changes in driving force and/or electronic coupling for underlying component redox reactions. Perhaps surprisingly, only a minor role for modifier-induced shifts in conduction-band-edge energy was found. The combination of DSC-efficiency-relevant effects engendered by the modifiers was found to vary substantially as a function of the chemical identity of the redox shuttle employed. While types of modifiers are effective, a challenge going forward will be to construct systems in ways in which the benefits of organic and inorganic modifiers can be exploited in fully additive, or even synergistic, fashion.

Katz, Michael J.↗

Atomic Layer-by-Layer Deposition of Platinum on Palladium Octahedra for Enhanced Catalysts toward the Oxygen Reduction Reaction

We systematically evaluated two different approaches to the syntheses of Pd@PtnL (n = 2–5) core–shell octahedra. We initially prepared the core–shell octahedra using a polyol-based route by titrating a Pt(IV) precursor into the growth solution containing Pd octahedral seeds at 200 °C through the use of a syringe pump. The number of Pt atomic layers could be precisely controlled from two to five by increasing the volume of the precursor solution while fixing the amount of seeds. We then demonstrated the synthesis of Pd@Pt nL octahedra using a water-based route at 95 °C through the one-shot injection of a Pt(II) precursor. Due to the large difference in reaction temperature, the Pd@Pt nL octahedra obtained via the water-based route showed sharper corners than their counterparts obtained through the polyol-based route. When compared to a commercial Pt/C catalyst based upon 3.2 nm Pt particles, the Pd@Pt nL octahedra prepared using both methods showed similar remarkable enhancement in terms of activity (both specific and mass) and durability toward the oxygen reduction reaction. These calculations based upon periodic, self-consistent density functional theory suggested that the enhancement in specific activity for the Pd@Pt nL octahedra could be attributed to the destabilization of OH on their Pt nL */Pd(111) surface relative to the {111} and {100} facets exposed on the surface of Pt/C. Finally. the destabilization of OH facilitates its hydrogenation, which was found to be the rate-limiting step of the oxygen reduction reaction on all these surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An antiferromagnetic diode effect in even-layered MnBi 2 Te 4

In a p–n junction, the separation of positive and negative charges leads to diode transport, in which charge flows in only one direction. Non-centrosymmetric polar conductors are intrinsic diodes that could be of use in the development of nonlinear applications. Such systems have recently been extended to non-centrosymmetric superconductors, and the superconducting diode effect has been observed. Here, in this paper, we report an antiferromagnetic diode effect in a centrosymmetric crystal without directional charge separation. We observed large second-harmonic transport in a nonlinear electronic device enabled by the compensated antiferromagnetic state of even-layered MnBi 2 Te 4 . We show that this antiferromagnetic diode effect can be used to create in-plane field-effect transistors and microwave-energy-harvesting devices. We also show that electrical sum-frequency generation can be used as a tool to detect nonlinear responses in quantum materials.

electronic properties and materials↗

Mechanical properties of irradiated single-layer graphene

The mechanical properties of irradiated single-layer graphene sheets are determined as a function of inserted vacancy concentration. We find that the vacancy-induced crystalline-to-amorphous transition is accompanied by a brittle-to-ductile transition in the failure response of irradiated graphene sheets for inserted vacancy concentrations of 8%-12%. While point defects and larger voids appreciably degrade the strength of pristine graphene, we find that even heavily damaged samples ({approx}20% vacancies) exhibit tensile strengths of {approx}30 GPa, in significant excess of those typical of engineering materials. Our results suggest that defect engineering of graphene is feasible without incurring a complete loss of its desirable mechanical properties.

36 MATERIALS SCIENCE↗

Thermal conductivity of Er{sup +3}:Y{sub 2}O{sub 3} films grown by atomic layer deposition

Cross-plane thermal conductivity of 800, 458, and 110 nm erbium-doped crystalline yttria (Er{sup +3}:Y{sub 2}O{sub 3}) films deposited via atomic layer deposition was measured using the 3ω method at room temperature. Thermal conductivity results show 16-fold increase in thermal conductivity from 0.49 W m{sup −1}K{sup −1} to 8 W m{sup −1}K{sup −1} upon post deposition annealing, partially due to the suppression of the number of the -OH/H{sub 2}O bonds in the films after annealing. Thermal conductivity of the annealed film was ∼70% lower than undoped bulk single crystal yttria. The cumulative interface thermal resistivity of substrate-Er{sup +3}:Y{sub 2}O{sub 3}-metal heater was determined to be ∼2.5 × 10{sup −8} m{sup 2} K/W.

36 MATERIALS SCIENCE↗

Biexciton formation and exciton coherent coupling in layered GaSe

Nonlinear two-dimensional Fourier transform (2DFT) and linear absorption spectroscopy are used to study the electronic structure and optical properties of excitons in the layered semiconductor GaSe. At the 1s exciton resonance, two peaks are identified in the absorption spectra, which are assigned to splitting of the exciton ground state into the triplet and singlet states. 2DFT spectra acquired for co-linear polarization of the excitation pulses feature an additional peak originating from coherent energy transfer between the singlet and triplet. At cross-linear polarization of the excitation pulses, the 2DFT spectra expose a new peak likely originating from bound biexcitons. The polarization dependent 2DFT spectra are well reproduced by simulations using the optical Bloch equations for a four level system, where many-body effects are included phenomenologically. Although biexciton effects are thought to be strong in this material, only moderate contributions from bound biexciton creation can be observed. The biexciton binding energy of ∼2 meV was estimated from the separation of the peaks in the 2DFT spectra. Temperature dependent absorption and 2DFT measurements, combined with “ab initio” theoretical calculations of the phonon spectra, indicate strong interaction with the A{sub 1}{sup ′} phonon mode. Excitation density dependent 2DFT measurements reveal excitation induced dephasing and provide a lower limit for the homogeneous linewidth of the excitons in the present GaSe crystal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the atmospheric boundary layer with integrated remote-sensing platforms during the American WAKE ExperimeNt (AWAKEN) campaign

The American WAKE ExperimeNt (AWAKEN) collaboration is an observational-based field campaign in northern Oklahoma intended to analyze the potential influence of onshore wind farms and their collective wakes on wind power production, turbine structural loads, and on the atmospheric boundary layer (ABL). Focusing on the ABL effects, the University of Oklahoma and the Lawrence Livermore National Laboratory collected continuous high-resolution kinematic and thermodynamic profile measurements during 2022 and Summer 2023. The deployment strategy for these campaigns is detailed first, followed by an initial comparison of data from two sites in the AWAKEN domain: a near-farm site to examine collective wake impacts on the ABL, and a far-field site remaining outside the wind farm-waked region. Here, we summarize the datasets available and demonstrate the benefits of these observations and multiple value-added products (VAPs) for investigation of ABL features observed during AWAKEN. We also highlight examples of preliminary analyses, including ABL height detection and nocturnal low-level jet examination, which are produced using novel VAPs based on optimal estimation to retrieve deeper Doppler lidar wind profiles than previously resolved, along with their uncertainty. By including the near-farm and far-field site in these analyses, we identified a pattern of stronger lower-atmospheric mixing at the near-farm site than the far-field site, motivating deeper investigation into the relationship between wind farms and general ABL characteristics. Future analysis will delve deeper into this relationship by examining other ABL characteristics, such as atmospheric stability and convection.

17 WIND ENERGY↗