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At least 1,675 records · Page 93

Leveraging Multiproton-Coupled Electron Transfer to Improve Ir(III) Photocatalyst Efficiency

In photoredox reactions, charge recombination (CR) limits quantum yields, hindering the efficient conversion of light energy into catalytic activity. To address this, we drew inspiration from redox relays in photosystem II (PSII) and developed a new series of iridium(III) complexes featuring covalently attached benzimidazole-phenol-pyridine (BIP-Py) groups to facilitate intramolecular multiproton-coupled electron transfer (MPCET). Herein, we evaluate the effects of MPCET through an extended and well-defined hydrogen-bond network to improve photocatalytic activity and mitigate rapid charge recombination. Infrared spectroelectrochemistry reveals pyridine protonation upon phenol oxidation, while visible spectroelectrochemistry and transient absorption spectroscopy confirm the electro- and photochemical formation of chargeseparated states (CSS) involving oxidized BIP, resulting from intramolecular proton-coupled electron transfer (PCET). The application of the BIP-Py platform in a photocatalytic Nhydroxyphthalimide ester reduction reaction resulted in a ∼106-fold reduction in CR rate and a quantum yield enhancement of up to 157%. Our findings suggest that incorporating MPCET-based redox relays into photocatalyst frameworks is an effective strategy to enhance the efficiency of photocatalytic systems.

Catalysts↗

Hole Transport in Nonstoichiometric and Doped Wüstite

We propose ways to enhance the conductivity of wustite (i.e., naturally p-type FeO), a visible-light-absorbing, inexpensive, abundant, and nontoxic potential alternative material for solar energy conversion devices. Unfortunately, the conversion efficiency of FeO is inhibited by its low hole conductivity. Increasing the iron vacancy concentration or adding p-type dopants improves FeO conductivity by increasing the number of holes; however, it is not known which strategy introduces larger energy traps that would hinder hole conductivity. Here we employ the small polaron model along with ab initio calculations on electrostatically embedded clusters to analyze the local trapping effects of iron vacancies and several substitutional p-type dopants that are soluble in FeO, including copper, nitrogen, lithium, and sodium, and also hydrogen as an interstitial dopant for comparison. We find that vacancies create stronger traps than dopants and that copper and nitrogen dopants form deeper traps than lithium, sodium, or hydrogen. Furthermore, hydrogen repels the hole and substantially decreases the trap formed by an iron vacancy. Because of the shallower traps formed compared to vacancies, lithium-, sodium-, or hydrogen-doped, nanostructured or alloyed FeO may be worth evaluating as a p-type semiconductor for solar energy conversion applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Highly efficient and electrically robust carbon irradiated semi-insulating GaAs based photoconductive terahertz emitters

We demonstrate here an efficient photoconductive THz source with low electrical power consumption. We have increased the maximum THz radiation power emitted from SI-GaAs based photoconductive emitters (PCEs) by two orders of magnitude. By irradiating the SI-GaAs substrate with Carbon-ions up to 2 μm deep, we have created lot of defects and decreased the lifetime of photo-excited carriers inside the substrate. Depending on the irradiation dose, we find 1 to 2 orders of magnitude decrease in total current flowing in the substrate, resulting in subsequent decrease of heat dissipation in the device. This has resulted in increasing maximum cut-off of the applied voltage across PCE electrodes to operate the device without thermal breakdown from ∼35 V to >150 V for the 25 μm electrode gaps. At optimum operating conditions, carbon irradiated (10{sup 14} ions/cm{sup 2}) PCEs give THz pulses with power about 100 times higher in comparison to the usual PCEs on SI-GaAs and electrical to THz power conversion efficiency has improved by a factor of ∼800.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Low-temperature high-mobility amorphous IZO for silicon heterojunction solar cells

Parasitic absorption in the transparent conductive oxide (TCO) front electrode is one of the limitations of silicon heterojunction (SHJ) solar cells efficiency. To avoid such absorption while retaining high conductivity, TCOs with high electron mobility are preferred over those with high carrier density. Here, we demonstrate improved SHJ solar cell efficiencies by applying high-mobility amorphous indium zinc oxide (a-IZO) as the front TCO. We sputtered a-IZO at low substrate temperature and low power density and investigated the optical and electrical properties, as well as subband tail formation-quantified by the Urbach energy (E U )-as a function of the sputtering oxygen partial pressure. We obtain an E U as low as 128 meV for films with the highest Hall mobility of 60 cm 2 /Vs. When comparing the performance of a-IZO films with indium tin oxide (ITO) and hydrogenated indium oxide (IO:H), we find that IO:H (115 cm 2 /Vs) exhibits a similar E U of 130 meV, while ITO (25 cm 2 /Vs) presents a much larger E U of up to 270 meV. The high film quality, indicated by the low E U , the high mobility, and low free carrier absorption of the developed a-IZO electrodes, result in a significant current improvement, achieving conversion efficiencies over 21.5%, outperforming those with standard ITO.

14 SOLAR ENERGY↗

Formation of solar cells based on Ba{sub 0.5}Sr{sub 0.5}TiO{sub 3} (BST) ferroelectric thick film

Growth of Ba{sub 0.5}Sr{sub 0.5}TiO{sub 3} (BST) 1 M thick films are conducted with variation of annealing hold time of 8 hours, 15 hours, 22 hours, and 29 hours at a constant temperature of 850 °C on p-type Si (100) substrate using sol-gel method then followed by spin coating process at 3000 rpm for 30 seconds. The BST thick film electrical conductivity is obtained to be 10{sup −5} to 10{sup −4} S/cm indicate that the BST thick film is classified as semiconductor material. The semiconductor energy band gap value of BST thick film based on annealing hold time of 8 hours, 15 hours, 22 hours, and 29 hours are 2.58 eV, 3.15 eV, 3.2 eV and 2.62 eV, respectively. The I-V photovoltaic characterization shows that the BST thick film is potentially solar cell device, and in accordance to annealing hold time of 8 hours, 15 hours, 22 hours and 29 hours have respective solar cell energy conversion efficiencies of 0.343%, 0.399%, 0.469% and 0.374%, respectively. Optical spectroscopy shows that BST thick film solar cells with annealing hold time of 8 hours, 15 hours, and 22 hours absorb effectively light energy at wavelength of ≥ 700 nm. BST film samples with annealing hold time of 29 hours absorb effectively light energy at wavelength of ≤ 700 nm. The BST thick film refraction index is between 1.1 to 1.8 at light wavelength between ±370 to 870 nm.

36 MATERIALS SCIENCE↗

Plasmon-enhanced polymer photovoltaic cells based on large aspect ratio gold nanorods and the related working mechanism

Two types of Au nanorods (NRs) possessing longitudinal/transverse axes of 55/11 (NR{sub 11}) and 90/18 nm (NR{sub 18}) are, respectively, incorporated into the hole extraction layer to improve optical-to-electrical conversion performances in polymer photovoltaic cells. Totally different improvement factors in short-circuit current and power conversion efficiency occur in the NR{sub 11}- and NR{sub 18}-doped cells. Optical simulations, electrical analysis, and morphology alteration accompanying with the incorporation of NRs were proceeded to investigate the reason, and analysis demonstrates that a slower damping of field around NRs{sub 18} (results in a field and absorption enhancement around the active layer) and one order higher scattering cross section in the NR{sub 18}-incorporated cell are key factors contributed to the improvement of cell performances.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Light potentials of photosynthetic energy storage in the field: what limits the ability to use or dissipate rapidly increased light energy?

The responses of plant photosynthesis to rapid fluctuations in environmental conditions are critical for efficient conversion of light energy. These responses are not well-seen laboratory conditions and are difficult to probe in field environments. We demonstrate an open science approach to this problem that combines multifaceted measurements of photosynthesis and environmental conditions, and an unsupervised statistical clustering approach. In a selected set of data on mint (Mentha sp.), we show that ‘light potentials’ for linear electron flow and non-photochemical quenching (NPQ) upon rapid light increases are strongly suppressed in leaves previously exposed to low ambient photosynthetically active radiation (PAR) or low leaf temperatures, factors that can act both independently and cooperatively. Further analyses allowed us to test specific mechanisms. With decreasing leaf temperature or PAR, limitations to photosynthesis during high light fluctuations shifted from rapidly induced NPQ to photosynthetic control of electron flow at the cytochrome b 6 f complex. At low temperatures, high light induced lumen acidification, but did not induce NPQ, leading to accumulation of reduced electron transfer intermediates, probably inducing photodamage, revealing a potential target for improving the efficiency and robustness of photosynthesis. We discuss the implications of the approach for open science efforts to understand and improve crop productivity.

59 BASIC BIOLOGICAL SCIENCES↗

Achieving a high open-circuit voltage in inverted wide-bandgap perovskite solar cells with a graded perovskite homojunction

Wide-bandgap (~1.7-1.8 eV) perovskite solar cells have attracted substantial research interest in recent years due to their great potential to fabricate efficient tandem solar cells via combining with a lower bandgap (1.1-1.3 eV) absorber (e.g., Si, copper indium gallium diselenide, or low-bandgap perovskite). However, wide-bandgap perovskite solar cells usually suffer from large open circuit voltage (V oc ) deficits caused by small grain sizes and photoinduced phase segregation. Here, we demonstrate that in addition to large grain sizes and passivated grain boundaries, controlling interface properties is critical for achieving high V oc 's in the inverted wide-bandgap perovskite solar cells. We adopt guanidinium bromide solution to tune the effective doping and electronic properties of the surface layer of perovskite thin films, leading to the formation of a graded perovskite homojunction. The enhanced electric field at the perovskite homojunction is revealed by Kelvin probe force microscopy measurements. This advance enables an increase in the V oc of the inverted perovskite solar cells from an initial 1.12 V to 1.24 V. With the optimization of the device fabrication process, the champion inverted wide-bandgap cell delivers a power conversion efficiency of 18.19% and sustains more than 72% of its initial efficiency after continuous illumination for 70 h without encapsulation. Additionally, a semitransparent device with an indium tin oxide back contact retains more than 88% of its initial efficiency after 100 h maximum power point tracking.

14 SOLAR ENERGY↗

Design and characterization of a solar-enhanced microwave plasma reactor for atmospheric pressure carbon dioxide decomposition

The decomposition of carbon dioxide (CO 2 ) is a main step in carbon re-utilization approaches aimed to fulfill fuels and chemicals demands and mitigate environmental emissions. Plasmachemical CO 2 decomposition processes can be highly efficient; however, their reliance on electrical energy can limit their economic viability and sustainability advantage. In contrast, solar thermochemical CO 2 decomposition approaches can have limited efficiency, but their direct use of the most abundant form of renewable energy affords them the greatest sustainability potential. Solar-Enhanced Microwave Plasma (SEMP) chemical synthesis, based on the direct interaction between microwave plasma and concentrated solar radiation, is investigated as a novel approach to combine the advantages of plasmachemical and solar thermochemical processes. SEMP is motivated by the potential for synergistic effects between solar photons and plasma species, implied by the markedly greater spectral absorption of nonequilibrium CO 2 plasma compared to that of equilibrium CO 2 , to lead to enhanced chemical decomposition. The design, development, and characterization of a SEMP reactor for atmospheric pressure CO 2 decomposition is presented. The reactor is powered by a 1.25 kW magnetron and by up to 525 W of incident radiative power from a high-flux solar simulator. Experimental results reveal that the microwave plasma absorbs up to 20% of concentrated solar radiation at a solar-to-electrical power ratio of 0.5, and that relative absorption decreases with increasing solar input power. Yet, conversion efficiency and plasma energy efficiency increase with increasing solar power, up to 9% and 25% respectively, for a solar-to-electrical power ratio of 0.75. The enhanced process performance appears to be a consequence of the greater power density in the plasma caused by the direct absorption of solar radiation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Increasing the Carbohydrate Output of Bamboo Using a Combinatorial Pretreatment

Bamboo represents a family of highly lignified biomass with significant resistance to cellulolytic enzyme degradation, and typically, a severe thermochemical pretreatment is needed to overcome its recalcitrance for producing fermentable sugars. Combinatorial pretreatments with a low holding temperature and low alkali dosage were investigated in this study in an attempt to remove the impediments to the accessibility of bamboo cellulose to enzymes and enable the efficient conversion of hemicellulose. Upon autohydrolysis at 180 °C, more than half of the hemicellulose (~58%) was solubilized, contributing to further delignification in the subsequent dilute alkali extraction (DAE). The solubilized hemicellulose mainly existed in the form of soluble xylan, which, after a novel endo-β-1,4-xylanase hydrolysis, generated a large amount of xylo-oligosaccharides with the xylobiose and xylotriose proportion reaching 72.99%. After the fractionation with combinatorial pretreatments, cellulose and xylose enzymatic hydrolysis yields were 73.36 and 86.98%, respectively, representing increments of 22.42 and 43.15% compared with the sole autohydrolysis process. Fluorescence microscopy (FM) and confocal Raman microscopy (CRM) images revealed that these dramatic improvements were caused by the deconstruction of the bamboo cell walls, including separation of the adjacent cell walls, removal of hemicellulose and lignin, migration and redistribution of lignin, and the increased exposure of cellulose. In addition, lignin chemical structure variations during the combinatorial pretreatment were analyzed with gel permeation chromatography (GPC), 2D HSQC NMR, and 31 P NMR, and the correlation between the lignin structure and enzymatic hydrolysis efficiency was investigated. In summary, this study highlighted the application of combinatorial pretreatments to maximize the carbohydrate output of bamboo and unveiled their mechanism that enabled the high-efficiency utilization of bamboo.

09 BIOMASS FUELS↗

Roll-to-Roll Printed Large-Area All-Polymer Solar Cells with 5% Efficiency Based on a Low Crystallinity Conjugated Polymer Blend

The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This particular methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm 2 . This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate.

36 MATERIALS SCIENCE↗

Microscopic subsurface characterization of layered magnetic materials using magnetic resonance force microscopy

This project resulted in the following accomplishments: 1) The invention of scanned probe ferromagnetic resonance microscopy. Upon implementation and refinement this approach was used to measure static and dynamic magnetic resonance properties of ferromagnets with an unprecedented combination of spectral and spatial resolution. 2) Demonstration and study of spin pumping in a pristine ferromagnet across a boundary defined entirely by a magnetic field gradient, and so free of materials discontinuities. 3) First demonstrated highly efficient dynamic spin injection from Y 3 Fe 5 O 12 (YIG) into NiO, an antiferromagnetic (AF) insulator and robust spin propagation in AF NiO over distances up to 100-nm thickness; both spin injection and spin transport are mediated by the AF spin correlations. 4) Demonstration of exceptionally high efficiency conversion of spin current to charge current achieved in spin pumping from the dynamic magnetization of a ferromagnetic insulator into a variety of adjacent metal films. 5) Seminal study of the nature of spin-orbit coupling in d-electron metals that revealed the dominant sensitivity of the d-orbital moment to the d-electron count and revealing the important roles of both d-electron configuration and atomic number in the physics of the spin Hall effect. 6) Demonstration of observation of FMR by means of optically-detected NV diamond relaxometry that provided a highly sensitive, spatially resolved FMR detection method and revealed spin pumping across 100-nm length scales by means of dipolar coupling. 7) Using magnetic field localization, developed for FMR imaging, demonstrated a novel approach to discretizing spin wave modes to improve the characteristics of auto-oscillators driven by pure spin currents produced by the spin Hall effect. 8) We demonstrated large spin pumping signals from propagating high wavevector spinwaves in thin film YIG find that the spin pumping efficiency was insensitive to wavevector thus emphasizing the promise of thin YIG films for spinwave-based spintronics by allowing for predictable down-scaling of device dimensions and enabling a broad range of operational frequencies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Surface Passivation and Carrier Collection in {110}, {100} and Circular Si Microwire Solar Cells

Surface recombination is a major bottleneck for realizing highly efficient micro/nanostructure solar cells. Parametric studies of the influence of Si microwire (SiMW) surface-facet orientation (rectangular with flat-facets, {110}, {100} and circular), with a fixed height of 10 µm, diameter (D = 1.5–9.5 µm), and sidewall spacing (S = 2.5–8.5 µm), and mesh-grid density (1–16 mm -2 ) on recombination and carrier collection in SiMW solar cells with radial p-n junctions are reported. An effective surface passivation layer composed of thin thermally grown silicon dioxide (SiO 2 ) and silicon nitride (SiN x ) layers is employed. For a fixed D of 1.5 µm, tight SiMW spacing results in improved short-circuit current density (J sc = 30.1 mA cm -2 ) and sparse arrays result in open-circuit voltages (V oc = 0.552 V) that are similar to those of control Si planar cells. For a fixed S, smaller D results in better light trapping at shorter wavelengths and higher J sc while larger D exhibits better light trapping at larger wavelengths and a higher V oc . With a mesh-grid electrode the power conversion efficiency increases to 15.3%. Finally, these results provide insights on the recombination mechanisms in SiMW solar cells and provide general design principles for optimizing their performance.

14 SOLAR ENERGY↗

Band Tailing and Deep Defect States in CH 3 NH 3 Pb(I 1–x Br x ) 3 Perovskites As Revealed by Sub-Bandgap Photocurrent

Organometal halide perovskite semiconductors have emerged as promising candidates for optoelectronic applications because of the outstanding charge carrier transport properties, achieved with low-temperature synthesis. In this paper, we present highly sensitive sub-bandgap external quantum efficiency (EQE) measurements of Au/spiro-OMeTAD/CH 3 NH 3 Pb(I 1–x Br x ) 3 /TiO 2 /FTO/glass photovoltaic devices. The room-temperature spectra show exponential band tails with a sharp onset characterized by low Urbach energies (E u ) over the full halide composition space. The Urbach energies are 15–23 meV, lower than those for most semiconductors with similar bandgaps (especially with E g > 1.9 eV). Intentional aging of CH 3 NH 3 Pb(I 1–x Br x ) 3 for up to 2300 h, reveals no change in E u , despite the appearance of the PbI 2 phase due to decomposition, and confirms a high degree of crystal ordering. Moreover, sub-bandgap EQE measurements reveal an extended band of sub-bandgap electronic states that can be fit with one or two point defects for pure CH 3 NH 3 PbI 3 or mixed CH 3 NH 3 Pb(I 1–x Br x ) 3 compositions, respectively. Finally, the study provides experimental evidence of defect states close to the midgap that could impact photocarrier recombination and energy conversion efficiency in higher bandgap CH 3 NH 3 Pb(I 1–x Br x ) 3 alloys.

36 MATERIALS SCIENCE↗

Using electron channeling contrast imaging to inform and improve the growth of high-efficiency GaAs solar cells on nanopatterned GaAs substrates

Patterned substrates provide opportunities for reducing the cost of high-efficiency III-V devices by incorporating mechanically weak layers beneficial for substrate reuse (e.g. by spalling). In this work, the functionality of electron channeling contrast imaging (ECCI) as a tool to efficiently understand and mitigate defect formation is exemplified by developing a process in which high-quality III-V material can be grown on nanopatterned GaAs substrates. Reactive ion etching used in the patterning process was found to damage the GaAs substrate surface, leading to the formation of stacking faults in the epitaxial material as observed by ECCI. Etching the patterned substrates in a 1 NH4OH: 1 H2O2: 50 DI H2O solution for 10 s prior to growth removed the substrate surface damage and stacking faults were no longer present. Growth of solar cell device structures initially produced samples with many macroscale flaws creating shunts in the devices, which complicated the assessment of material quality by device measurements. However, ECCI revealed that the epitaxial material surrounding macroscale flaws was free from any crystallographic defects such as stacking faults and threading dislocations. With this knowledge, we focused on refining the patterning process to eliminate the macroscale flaws. Solar cells were then grown on the improved nanopatterned substrates and exhibited device structures with defect densities less than 5 x 105 cm -2 and average conversion efficiency of 24.8%, nearly identical to devices grown on unpatterned epi-ready substrates (25.0%).

14 SOLAR ENERGY↗

Side Chain and Solvent Direction of Film Morphology in Small-Molecule Organic Solar Materials

Film morphology control is essential to materials development for efficient organic solar cells (OSCs). Unlocking methods to optimize the film morphology for materials without changing the fundamental electronic characteristics can enable previously unacceptable materials to achieve high performance. In this work, a series of acceptor-donor-acceptor (ADA) small molecule p-type OSC semiconductors having benzo[1,2-b:6,5-b0]dithiophene (bBDT) donor units and thiophene capped diketopyrrolopyrrole (TDPP) acceptor units are examined where the sole molecular design variation is in the electronically inactive side chains. Four bBDT(TDPP) 2 compounds with all possible combinations of either 2-ethelhexyl (EH), or 3,7-dimtheyloctyl (DMO) side chains on the bBDT core and TDPP units are discussed. When processed from a chloroform (CF)-only solution, blend films of the molecules with the PC 71 BM electron acceptor exhibit similar thin film properties and photovoltaic performance, regardless of the side chain composition. However, when the additive 1,8-diiodooctane (DIO) is included in the processing solution, the morphological properties and OSC performance diverge dramatically, with the side chain variations now dictating the film morphology, resulting in a >400% spread in power conversion efficiency (PCE). Donor molecules with a mixed side chain motif having the larger DMO side chain on the bBDT core unit deliver the best performance owing to greater donor:acceptor phase intermixing while maintaining contiguous and efficient charge transport pathways. Using in situ GIWAXS during spin-coating, it is shown that DIO extends crystallization times, thereby promoting more thermodynamically driven structures where the side chain compositions have greater impact. Lastly, general guidelines are presented for achieving morphological optimization via combined side chain engineering and processing additives.

36 MATERIALS SCIENCE↗

Photon–photon chemical thermodynamics of frequency conversion processes in highly multimode systems

Abstract Frequency generation in highly multimode nonlinear optical systems is inherently a complex process, giving rise to an exceedingly convoluted landscape of evolution dynamics. While predicting and controlling the global conversion efficiencies in such nonlinear environments has long been considered impossible, here, we formally address this challenge even in scenarios involving a very large number of spatial modes. By utilizing fundamental notions from optical statistical mechanics, we develop a universal theoretical framework that effectively treats all frequency components as chemical reactants/products, capable of undergoing optical thermodynamic reactions facilitated by a variety of multi-wave mixing effects. These photon–photon reactions are governed by conservation laws that directly determine the optical temperatures and chemical potentials of the ensued chemical equilibria for each frequency species. In this context, we develop a comprehensive stoichiometric model and formally derive an expression that relates the chemical potentials to the optical stoichiometric coefficients, in a manner akin to atomic/molecular chemical reactions. This advancement unlocks new predictive capabilities that can facilitate the optimization of frequency generation in highly multimode photonic arrangements, surpassing the limitations of conventional schemes that rely exclusively on nonlinear optical dynamics. Notably, we identify a universal regime of Rayleigh–Jeans thermalization where an optical reaction at near-zero optical temperatures can promote the complete and entropically irreversible conversion of light to the fundamental mode at a target frequency. Our theoretical results are corroborated by numerical simulations in settings where second-harmonic generation, sum-frequency generation and four-wave mixing processes can manifest.

Optics↗