30 research outputs found
Imaging material functionality through 3D nanoscale tracking of energy flow
The ability of energy carriers to move between atoms and molecules underlies
biochemical and material function. Understanding and controlling energy flow,
however, requires observing it on ultrasmall and ultrafast spatiotemporal
scales, where energetic and structural roadblocks dictate the fate of energy
carriers. Here we developed a non-invasive optical scheme that leverages
non-resonant interferometric scattering to track tiny changes in material
polarizability created by energy carriers. We thus map evolving energy carrier
distributions in four dimensions of spacetime with few-nanometer lateral
precision and directly correlate to material morphology. We visualize exciton,
charge, and heat transport in polyacene, silicon and perovskite semiconductors
and elucidate how disorder affects energy flow in 3D. For example, we show that
morphological boundaries in polycrystalline metal halide perovskites possess
lateral- and depth-dependent resistivities, blocking lateral transport for
surface but not bulk carriers. We furthermore reveal strategies to interpret
energy transport in disordered environments that will direct the design of
defect-tolerant materials for the semiconductor industry of tomorrow
(13)C or Not (13)C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides.
Asymmetric isotopic labeling of parallel and identical electron- or energy-transfer pathways in symmetrical molecular assemblies is an extremely challenging task owing to the inherent lack of isotopic selectivity in conventional synthetic methods. Yet, it would be a highly valuable tool in the study and control of complex light-matter interactions in molecular systems by exclusively and nonintrusively labeling one of otherwise identical reaction pathways, potentially directing charge and energy transport along a chosen path. Here we describe the first selective synthetic route to asymmetrically labeled organometallic compounds, on the example of charge-transfer platinum(II) cis-acetylide complexes. We demonstrate the selective (13)C labeling of one of two acetylide groups. We further show that such isotopic labeling successfully decouples the two ν(C≡C) in the mid-IR region, permitting independent spectroscopic monitoring of two otherwise identical electron-transfer pathways, along the (12)C≡(12)C and (13)C≡(13)C coordinates. Quantum-mechanical mixing leads to intriguing complex features in the vibrational spectra of such species, which we successfully model by full-dimensional anharmonically corrected DFT calculations, despite the large size of these systems. The synthetic route developed and demonstrated herein should lead to a great diversity of asymmetric organometallic complexes inaccessible otherwise, opening up a plethora of opportunities to advance the fundamental understanding and control of light-matter interactions in molecular systems
Exploring excited states of Pt(ii) diimine catecholates for photoinduced charge separation
The intense absorption in the red part of the visible range, and the presence of a lowest charge-transfer excited state, render Platinum(II) diimine catecholates potentially promising candidates for light-driven applications. Here, we test their potential as sensitisers in dye-sensitised solar cells and apply, for the first time, the sensitive method of photoacoustic calorimetry (PAC) to determine the efficiency of electron injection in the semiconductor from a photoexcited Pt(II) complex. Pt(II) catecholates containing 2,2′-bipyridine-4,4′-di-carboxylic acid (dcbpy) have been prepared from their parent iso-propyl ester derivatives, complexes of 2,2′-bipyridine-4,4′-di-C(O)OiPr, (COOiPr)2bpy, and their photophysical and electrochemical properties studied. Modifying diimine Pt(II) catecholates with carboxylic acid functionality has allowed for the anchoring of these complexes to thin film TiO2, where steric bulk of the complexes (3,5-ditBu-catechol vs. catechol) has been found to significantly influence the extent of monolayer surface coverage. Dye-sensitised solar cells using Pt(dcbpy)(tBu2Cat), 1a, and Pt(dcbpy)(pCat), 2a, as sensitisers, have been assembled, and photovoltaic measurements performed. The observed low, 0.02–0.07%, device efficiency of such DSSCs is attributed at least in part to the short excited state lifetime of the sensitisers, inherent to this class of complexes. The lifetime of the charge-transfer ML/LLCT excited state in Pt((COOiPr)2bpy)(3,5-di-tBu-catechol) was determined as 250 ps by picosecond time-resolved infrared spectroscopy, TRIR. The measured increase in device efficiency for 2a over 1a is consistent with a similar increase in the quantum yield of charge separation (where the complex acts as a donor and the semiconductor as an acceptor) determined by PAC, and is also proportional to the increased surface loading achieved with 2a. It is concluded that the relative efficiency of devices sensitised with these particular Pt(II) species is governed by the degree of surface coverage. Overall, this work demonstrates the use of Pt(diimine)(catecholate) complexes as potential photosensitizers in solar cells, and the first application of photoacoustic calorimetry to Pt(II) complexes in general
Quasi-phase-matched up- and down-conversion in periodically poled layered semiconductors
Nonlinear optics lies at the heart of classical and quantum light generation.
The invention of periodic poling revolutionized nonlinear optics and its
commercial applications by enabling robust quasi-phase-matching in crystals
such as lithium niobate. However, reaching useful frequency conversion
efficiencies requires macroscopic dimensions, limiting further technology
development and integration. Here we realize a periodically poled van der Waals
semiconductor (3R-MoS). Due to its exceptional nonlinearity, we achieve
macroscopic frequency conversion efficiency over a microscopic thickness of
only 1.2m, thinner than current systems with similar
performances. Due to unique intrinsic cavity effects, the thickness-dependent
quasi-phase-matched second harmonic signal surpasses the usual quadratic
enhancement by . Further, we report the broadband generation of photon
pairs at telecom wavelengths via quasi-phase-matched spontaneous parametric
down-conversion. This work opens the new and unexplored field of phase-matched
nonlinear optics with microscopic van der Waals crystals, unlocking
applications that require simple, ultra-compact technologies such as on-chip
entangled photon-pair sources for integrated quantum circuitry and sensing
Electronic interactions in Dirac fluids visualized by nano-terahertz spacetime mapping
Ultraclean graphene at charge neutrality hosts a quantum critical Dirac fluid
of interacting electrons and holes. Interactions profoundly affect the charge
dynamics of graphene, which is encoded in the properties of its collective
modes: surface plasmon polaritons (SPPs). The group velocity and lifetime of
SPPs have a direct correspondence with the reactive and dissipative parts of
the tera-Hertz (THz) conductivity of the Dirac fluid. We succeeded in tracking
the propagation of SPPs over sub-micron distances at femto-second (fs) time
scales. Our experiments uncovered prominent departures from the predictions of
the conventional Fermi-liquid theory. The deviations are particularly strong
when the densities of electrons and holes are approximately equal. Our imaging
methodology can be used to probe the electromagnetics of quantum materials
other than graphene in order to provide fs-scale diagnostics under
near-equilibrium conditions
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Considerations for reducing food system energy demand while scaling up urban agriculture
There is an increasing global interest in scaling up urban agriculture (UA) in its various forms, from private gardens to sophisticated commercial operations. Much of this interest is in the spirit of environmental protection, with reduced waste and transportation energy highlighted as some of the proposed benefits of UA; however, explicit consideration of energy and resource requirements needs to be made in order to realize these anticipated environmental benefits. A literature review is undertaken here to provide new insight into the energy implications of scaling up UA in cities in high-income countries, considering UA classification, direct/indirect energy pressures, and
interactions with other components of the food–energy–water nexus. This is followed by an exploration of ways in which these cities can plan for the exploitation of waste flows for resource-efficient UA.
Given that it is estimated that the food system contributes nearly 15% of total US energy demand, optimization of resource use in food production, distribution, consumption, and waste systems may have a significant energy impact. There are limited data available that quantify resource demand implications directly associated with UA systems, highlighting that the literature is not yet sufficiently
robust to make universal claims on benefits. This letter explores energy demand from conventional resource inputs, various production systems, water/energy trade-offs, alternative irrigation, packaging materials, and transportation/supply chains to shed light on UA-focused research needs.
By analyzing data and cases from the existing literature, we propose that gains in energy efficiency could be realized through the co-location of UA operations with waste streams (e.g. heat, CO2, greywater, wastewater, compost), potentially increasing yields and offsetting life cycle energy demands relative to conventional approaches. This begs a number of energy-focused UA research questions that explore the opportunities for integrating the variety of UA structures and technologies, so that they are better able to exploit these urban waste flows and achieve whole-system reductions in energy demand. Any planning approach to implement these must, as always, assess how context will
influence the viability and value added from the promotion of UA
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Imaging material functionality through three-dimensional nanoscale tracking of energy flow.
The ability of energy carriers to move between atoms and molecules underlies biochemical and material function. Understanding and controlling energy flow, however, requires observing it on ultrasmall and ultrafast spatio-temporal scales, where energetic and structural roadblocks dictate the fate of energy carriers. Here, we developed a non-invasive optical scheme that leverages non-resonant interferometric scattering to track tiny changes in material polarizability created by energy carriers. We thus map evolving energy carrier distributions in four dimensions of spacetime with few-nanometre lateral precision and directly correlate them with material morphology. We visualize exciton, charge and heat transport in polyacene, silicon and perovskite semiconductors and elucidate how disorder affects energy flow in three dimensions. For example, we show that morphological boundaries in polycrystalline metal halide perovskites possess lateral- and depth-dependent resistivities, blocking lateral transport for surface but not bulk carriers. We also reveal strategies for interpreting energy transport in disordered environments that will direct the design of defect-tolerant materials for the semiconductor industry of tomorrow
Recommended from our members
Imaging material functionality through three-dimensional nanoscale tracking of energy flow.
The ability of energy carriers to move between atoms and molecules underlies biochemical and material function. Understanding and controlling energy flow, however, requires observing it on ultrasmall and ultrafast spatio-temporal scales, where energetic and structural roadblocks dictate the fate of energy carriers. Here, we developed a non-invasive optical scheme that leverages non-resonant interferometric scattering to track tiny changes in material polarizability created by energy carriers. We thus map evolving energy carrier distributions in four dimensions of spacetime with few-nanometre lateral precision and directly correlate them with material morphology. We visualize exciton, charge and heat transport in polyacene, silicon and perovskite semiconductors and elucidate how disorder affects energy flow in three dimensions. For example, we show that morphological boundaries in polycrystalline metal halide perovskites possess lateral- and depth-dependent resistivities, blocking lateral transport for surface but not bulk carriers. We also reveal strategies for interpreting energy transport in disordered environments that will direct the design of defect-tolerant materials for the semiconductor industry of tomorrow