Publisher Correction: Cleavable comonomers enable degradable, recyclable thermoset plastics.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Cleavable comonomers enable degradable, recyclable thermoset plastics.

Thermosets-polymeric materials that adopt a permanent shape upon curing-have a key role in the modern plastics and rubber industries, comprising about 20 per cent of polymeric materials manufactured today, with a worldwide annual production of about 65 million tons1,2. The high density of crosslinks that gives thermosets their useful properties (for example, chemical and thermal resistance and tensile strength) comes at the expense of degradability and recyclability. Here, using the industrial thermoset polydicyclopentadiene as a model system, we show that when a small number of cleavable bonds are selectively installed within the strands of thermosets using a comonomer additive in otherwise traditional curing workflows, the resulting materials can display the same mechanical properties as the native material, but they can undergo triggered, mild degradation to yield soluble, recyclable products of controlled size and functionality. By contrast, installation of cleavable crosslinks, even at much higher loadings, does not produce degradable materials. These findings reveal that optimization of the cleavable bond location can be used as a design principle to achieve controlled thermoset degradation. Moreover, we introduce a class of recyclable thermosets poised for rapid deployment.

Nonlinear rotational spectroscopy reveals many-body interactions in water molecules.

Because of their central importance in chemistry and biology, water molecules have been the subject of decades of intense spectroscopic investigations. Rotational spectroscopy of water vapor has yielded detailed information about the structure and dynamics of isolated water molecules, as well as water dimers and clusters. Nonlinear rotational spectroscopy in the terahertz regime has been developed recently to investigate the rotational dynamics of linear and symmetric-top molecules whose rotational energy levels are regularly spaced. However, it has not been applied to water or other lower-symmetry molecules with irregularly spaced levels. We report the use of recently developed two-dimensional (2D) terahertz rotational spectroscopy to observe high-order rotational coherences and correlations between rotational transitions that were previously unobservable. The results include two-quantum (2Q) peaks at frequencies that are shifted slightly from the sums of distinct rotational transitions on two different molecules. These results directly reveal the presence of previously unseen metastable water complexes with lifetimes of 100 ps or longer. Several such peaks observed at distinct 2Q frequencies indicate that the complexes have multiple preferred bimolecular geometries. Our results demonstrate the sensitivity of rotational correlations measured in 2D terahertz spectroscopy to molecular interactions and complexation in the gas phase.

Nanotwinning-assisted dynamic recrystallization at high strains and strain rates.

Grain refinement is a widely sought-after feature of many metal production processes and frequently involves a process of recrystallization. Some processing methods use very high strain rates and high strains to refine the grain structure into the nanocrystalline regime. However, grain refinement processes are not clear in these extreme conditions, which are hard to study systematically. Here, we access those extreme conditions of strain and strain rate using single copper microparticle impact events with a laser-induced particle impact tester. Using a combined dictionary-indexing electron backscatter diffraction and scanning transmission electron microscopy approach for postmortem characterization of impact sites, we systematically explore increasing strain levels and observe a recrystallization process that is facilitated by nanotwinning, which we term nanotwinning-assisted dynamic recrystallization. It achieves much finer grain sizes than established modes of recrystallization and therefore provides a pathway to the finest nanocrystalline grain sizes through extreme straining processes.

High-power laser beam shaping using a metasurface for shock excitation and focusing at the microscale.

Achieving high repeatability and efficiency in laser-induced strong shock wave excitation remains a significant technical challenge, as evidenced by the extensive efforts undertaken at large-scale national laboratories to optimize the compression of light element pellets. In this study, we propose and model a novel optical design for generating strong shocks at a tabletop scale. Our approach leverages the spatial and temporal shaping of multiple laser pulses to form concentric laser rings on condensed matter samples. Each laser ring initiates a two-dimensional focusing shock wave that overlaps and converges with preceding shock waves at a central point within the ring. We present preliminary experimental results for a single ring configuration. To enable high-power laser focusing at the micron scale, we demonstrate experimentally the feasibility of employing dielectric metasurfaces with exceptional damage threshold, experimentally determined to be 1.1 J/cm2, as replacements for conventional optics. These metasurfaces enable the creation of pristine, high-fluence laser rings essential for launching stable shock waves in materials. Herein, we showcase results obtained using a water sample, achieving shock pressures in the gigapascal (GPa) range. Our findings provide a promising pathway towards the application of laser-induced strong shock compression in condensed matter at the microscale.

Nonlinear Optical Absorption in Nanoscale Films Revealed through Ultrafast Acoustics.

Herein we describe a novel spinning pump-probe photoacoustic technique developed to study nonlinear absorption in thin films. As a test case, an organic polycrystalline thin film of quinacridone, a well-known pigment, with a thickness in the tens of nanometers range, is excited by a femtosecond laser pulse which generates a time-domain Brillouin scattering signal. This signal is directly related to the strain wave launched from the film into the substrate and can be used to quantitatively extract the nonlinear optical absorption properties of the film itself. Quinacridone exhibits both quadratic and cubic laser fluence dependence regimes which we show to correspond to two- and three-photon absorption processes. This technique can be broadly applied to materials that are difficult or impossible to characterize with conventional transmittance-based measurements including materials at the nanoscale, prone to laser damage, with very weak nonlinear properties, opaque, or highly scattering.

Terahertz Field-Induced Reemergence of Quenched Photoluminescence in Quantum Dots.

The continuous and concerted development of colloidal quantum dot light-emitting diodes over the past two decades has established them as a bedrock technology for the next generation of displays. However, a fundamental issue that limits the performance of these devices is the quenching of photoluminescence due to excess charges from conductive charge transport layers. Although device designs have leveraged various workarounds, doing so often comes at the cost of limiting efficient charge injection. Here we demonstrate that high-field terahertz (THz) pulses can dramatically brighten quenched QDs on metallic surfaces, an effect that persists for minutes after THz irradiation. This phenomenon is attributed to the ability of the THz field to remove excess charges, thereby reducing trion and nonradiative Auger recombination. Our findings show that THz technologies can be used to suppress and control such undesired nonradiative decay, potentially in a variety of luminescent materials for future device applications.

Supersonic impact resilience of nanoarchitected carbon.

Architected materials with nanoscale features have enabled extreme combinations of properties by exploiting the ultralightweight structural design space together with size-induced mechanical enhancement at small scales. Apart from linear waves in metamaterials, this principle has been restricted to quasi-static properties or to low-speed phenomena, leaving nanoarchitected materials under extreme dynamic conditions largely unexplored. Here, using supersonic microparticle impact experiments, we demonstrate extreme impact energy dissipation in three-dimensional nanoarchitected carbon materials that exhibit mass-normalized energy dissipation superior to that of traditional impact-resistant materials such as steel, aluminium, polymethyl methacrylate and Kevlar. In-situ ultrahigh-speed imaging and post-mortem confocal microscopy reveal consistent mechanisms such as compaction cratering and microparticle capture that enable this superior response. By analogy to planetary impact, we introduce predictive tools for crater formation in these materials using dimensional analysis. These results substantially uncover the dynamic regime over which nanoarchitecture enables the design of ultralightweight, impact-resistant materials that could open the way to design principles for lightweight armour, protective coatings and blast-resistant shields for sensitive electronics.

High-speed two-dimensional terahertz spectroscopy with echelon-based shot-to-shot balanced detection.

By using a reflective-echelon-based electro-optic sampling technique and a fast detector, we develop a two-dimensional terahertz (THz) spectrometer capable of shot-to-shot balanced readout of THz waveforms at a full 1-kHz repetition rate. To demonstrate the capabilities of this new detection scheme for high-throughput applications, we use gas-phase acetonitrile as a model system to acquire two-dimensional THz rotational spectra. The results show a two-order-of-magnitude speedup in the acquisition of multidimensional THz spectra when compared to conventional delay-scan methods while maintaining accurate retrieval of the nonlinear THz signal. Our report presents a feasible solution for bringing the technique of multidimensional THz spectroscopy into widespread practice.

Nanoscale Transient Magnetization Gratings Created and Probed by Femtosecond Extreme Ultraviolet Pulses.

We utilize coherent femtosecond extreme ultraviolet (EUV) pulses from a free electron laser (FEL) to generate transient periodic magnetization patterns with periods as short as 44 nm. Combining spatially periodic excitation with resonant probing at the M-edge of cobalt allows us to create and probe transient gratings of electronic and magnetic excitations in a CoGd alloy. In a demagnetized sample, we observe an electronic excitation with a rise time close to the FEL pulse duration and ∼0.5 ps decay time indicative of electron-phonon relaxation. When the sample is magnetized to saturation in an external field, we observe a magnetization grating, which appears on a subpicosecond time scale as the sample is demagnetized at the maxima of the EUV intensity and then decays on the time scale of tens of picoseconds via thermal diffusion. The described approach opens multiple avenues for studying dynamics of ultrafast magnetic phenomena on nanometer length scales.

Room Temperature Terahertz Electroabsorption Modulation by Excitons in Monolayer Transition Metal Dichalcogenides.

The interaction between off-resonant laser pulses and excitons in monolayer transition metal dichalcogenides is attracting increasing interest as a route for the valley-selective coherent control of the exciton properties. Here, we extend the classification of the known off-resonant phenomena by unveiling the impact of a strong THz field on the excitonic resonances of monolayer MoS2. We observe that the THz pump pulse causes a selective modification of the coherence lifetime of the excitons, while keeping their oscillator strength and peak energy unchanged. We rationalize these results theoretically by invoking a hitherto unobserved manifestation of the Franz-Keldysh effect on an exciton resonance. As the modulation depth of the optical absorption reaches values as large as 0.05 dB/nm at room temperature, our findings open the way to the use of semiconducting transition metal dichalcogenides as compact and efficient platforms for high-speed electroabsorption devices.

Macroscopic Ionic Flow in a Superionic Conductor Na

Ionic motion significantly contributes to conductivity in devices such as memory, switches, and rechargeable batteries. In our work, we experimentally demonstrate that intense terahertz electric-field transients can be used to manipulate ions in a superionic conductor, namely Na^{+} ß-alumina. The cations trapped in the local potential minima are accelerated using single-cycle terahertz pulses, thereby inducing a macroscopic current flow on a subpicosecond timescale. Our results clearly show that single-cycle terahertz pulses can be used to significantly modulate the nature of superionic conductors and could possibly serve as a basic tool for application in future electronic devices.

Pressure-Thresholded Response in Cylindrically Shocked Cyclotrimethylene Trinitramine (RDX).

We demonstrate a strongly thresholded response in cyclotrimethylene trinitramine (RDX) when it is cylindrically shocked using a novel waveguide geometry. Using ultrafast single-shot multi-frame imaging, we demonstrate that <100 µm diameter single crystals of RDX embedded in a polymer host deform along preferential planes for >100 ns after the shock first arrives in the crystal. We use in situ imaging and time-resolved photoemission to demonstrate that short-lived chemistry occurs with complex deformation pathways. Using scanning electron microscopy and ultra-small-angle X-ray scattering, we demonstrate that the shock-induced dynamics leave behind porous crystals, with pore shapes and sizes that change significantly with shock pressure. A threshold pressure of ∼12 GPa at the center of convergence separated the single-mode planar crystal deformations from the chemistry-coupled multi-plane dynamics at higher pressures. Our observations indicate preferential directions for deformation in our cylindrically shocked system, despite the applied stress along many different crystallographic planes.

Crystalline-like ordering of 8CB liquid crystals revealed by time-domain Brillouin scattering.

We demonstrate that time-domain Brillouin scattering (TDBS), a technique based on an ultrafast pump-probe approach, is sensitive to phase transitions and apply it to the study of structural changes in 8CB liquid crystals at different temperatures across the isotropic, nematic, smectic, and crystalline phases. We investigate the viscoelastic properties of 8CB squeezed in a narrow gap, from the nanometer to submicrometer thickness range, and conclude on the long-range molecular structuring of the smectic phase. These TDBS results reveal that confinement effects favor structuring of the smectic phase into a crystallinelike phase that can be observed at wide distances far beyond the molecular dimensions.

Toward broadband mechanical spectroscopy.

Diverse material classes exhibit qualitatively similar behavior when made viscous upon cooling toward the glass transition, suggesting a common theoretical basis. We used seven different measurement methods to determine the mechanical relaxation kinetics of a prototype molecular glass former over a temporal range of 13 decades and over a temperature range spanning liquid to glassy states. The data conform to time-temperature superposition for the main (alpha) process and to a scaling relation of schematic mode-coupling theory. The broadband mechanical measurements demonstrated have fundamental and practical applications in polymer science, geophysics, multifunctional materials, and other areas.

Terahertz-Driven Stark Spectroscopy of CdSe and CdSe-CdS Core-Shell Quantum Dots.

The effects of large external fields on semiconductor nanostructures could reveal much about field-induced shifting of electronic states and their dynamical responses and could enable electro-optic device applications that require large and rapid changes in optical properties. Studies of quasi-dc electric field modulation of quantum dot (QD) properties have been limited by electrostatic breakdown processes observed under high externally applied field levels. To circumvent this, here we apply ultrafast terahertz (THz) electric fields with switching times on the order of 1 ps. We show that a pulsed THz electric field, enhanced by a microslit field enhancement structure (FES), can strongly manipulate the optical absorption properties of a thin film of CdSe and CdSe-CdS core-shell QDs on the subpicosecond time scale with spectral shifts that span the visible to near-IR range. Numerical simulations using a semiempirical tight binding model show that the band gap of the QD film can be shifted by as much a 79 meV during these time scales. The results allow a basic understanding of the field-induced shifting of electronic levels and suggest electro-optic device applications.

Analysis of terahertz generation by beamlet superposition.

A theory of terahertz generation using a superposition of beamlets is developed. It is shown how such an arrangement produces a distortion-free tilted pulse front. We analytically show how a superposition of beamlets produces terahertz radiation with greater efficiency and spatial homogeneity compared to tilted pulse fronts generated by diffraction gratings. The advantages are particularly notable for large pump bandwidths and beam sizes, suggesting better performance in the presence of cascading effects and for high energy pumping. Closed-form expressions for terahertz spectra and transients in three spatial dimensions are derived. Conditions for obtaining performance better than conventional tilted pulse fronts and bounds for optimal pump parameters are furnished.

Dynamics of a Persistent Insulator-to-Metal Transition in Strained Manganite Films.

Transition metal oxides possess complex free-energy surfaces with competing degrees of freedom. Photoexcitation allows shaping of such rich energy landscapes. In epitaxially strained La_{0.67}Ca_{0.33}MnO_{3}, optical excitation with a sub-100-fs pulse above 2 mJ/cm^{2} leads to a persistent metallic phase below 100 K. Using single-shot optical and terahertz spectroscopy, we show that this phase transition is a multistep process. We conclude that the phase transition is driven by partial charge-order melting, followed by growth of the persistent metallic phase on longer timescales. A time-dependent Ginzburg-Landau model can describe the fast dynamics of the reflectivity, followed by longer timescale in-growth of the metallic phase.

Nonlinear two-dimensional terahertz photon echo and rotational spectroscopy in the gas phase.

Ultrafast 2D spectroscopy uses correlated multiple light-matter interactions for retrieving dynamic features that may otherwise be hidden under the linear spectrum; its extension to the terahertz regime of the electromagnetic spectrum, where a rich variety of material degrees of freedom reside, remains an experimental challenge. We report a demonstration of ultrafast 2D terahertz spectroscopy of gas-phase molecular rotors at room temperature. Using time-delayed terahertz pulse pairs, we observe photon echoes and other nonlinear signals resulting from molecular dipole orientation induced by multiple terahertz field-dipole interactions. The nonlinear time domain orientation signals are mapped into the frequency domain in 2D rotational spectra that reveal J-state-resolved nonlinear rotational dynamics. The approach enables direct observation of correlated rotational transitions and may reveal rotational coupling and relaxation pathways in the ground electronic and vibrational state.

Efficient terahertz generation in highly nonlinear organic crystal HMB-TMS.

We report on generation of strong and broadband terahertz (THz) pulses via collinearly phase-matched optical rectification of near-infrared femtosecond pulses in the organic nonlinear optical HMB-TMS (2-(4-hydroxy-3-methoxystyryl)-3-methylbenzo[d]thiazol-3-ium 2,4,6-trimethylbenzenesulfonate) single crystals which exhibit optimal molecular orientation and large macroscopic optical nonlinearity for efficient THz wave generation. Single-cycle THz pulses with a peak electric field strength of 0.66 MV/cm and a bandwidth from 0.1 to 5.4 THz are achieved from an HMB-TMS crystal with only a 2-mm clear aperture pumped by 1350 nm pulses at moderate fluences. The generated THz energy is about 1 µJ and the corresponding pump-to-THz energy conversion efficiency reaches 0.23%.