Phonon-assisted formation of an itinerant electronic density wave by Jiaruo in Nature Communications Physics
Electronic instabilities drive ordering transitions in condensed matter. Despite many advances in the microscopic understanding of the ordered states, a more nuanced and profound question often remains unanswered: how do the collective excitations influence the electronic order formation? Here, we experimentally show that a phonon affects the spin density wave (SDW) formation after an SDW-quench by femtosecond laser pulses. In a thin film, the temperature-dependent SDW period is quantized, allowing us to track the out-of-equilibrium formation path of the SDW precisely. By exploiting its persistent coupling to the lattice, we probe the SDW through the transient lattice distortion, measured by femtosecond X-ray diffraction. We find that within 500 femtoseconds after a complete quench, the SDW forms with the low-temperature period, directly bypassing a thermal state with the high-temperature period. We argue that a wavevector-matched phonon launched by the quench changes the formation path of the SDW through the dynamic pinning of the order parameter.
Cornell Chronicle Feature on Disorder Dynamics in Battery Nanoparticles During Phase Transitions Revealed by Operando Single-Particle Diffraction by Jason in Advanced Energy Materials
Structural and ion-ordering phase transitions limit the viability of sodium-ion intercalation materials in grid scale battery storage by reducing their lifetime. However, the combination of phenomena in nanoparticulate electrodes creates complex behavior that is difficult to investigate, especially on the single-nanoparticle scale under operating conditions. In this work, operando single-particle X-ray diffraction (oSP-XRD) is used to observe single-particle rotation, interlayer spacing, and layer misorientation in a functional sodium-ion battery. oSP-XRD is applied to Na2/3Ni1/3Mn2/3O2, an archetypal P2-type sodium-ion-positive electrode material with the notorious P2-O2 phase transition induced by sodium (de)intercalation. It is found that during sodium extraction, the misorientation of crystalline layers inside individual particles increases before the layers suddenly align just prior to the P2-O2 transition. The increase in the long-range order coincides with an additional voltage plateau signifying a phase transition prior to the P2-O2 transition. To explain the layer alignment, a model for the phase evolution is proposed that includes a transition from localized to correlated Jahn–Teller distortions. The model is anticipated to guide further characterization and engineering of sodium-ion intercalation materials with P2-O2 type transitions. oSP-XRD, therefore, opens a powerful avenue for revealing complex phase behavior in heterogeneous nanoparticulate systems.
The relationship between charge transport and structural transformations dictates the properties of electrochemical systems. Despite their importance, the reduction–oxidation (redox) reactions within dynamically coexisting structures have so far eluded direct operando investigation. Here, we use resonant X-ray scattering to select X-ray spectra of a crystal structure coexisting with a different structure during a redox-induced phase transformation in P2-Na2/3Ni1/3Mn2/3O2. The spectra of the P2 structure become static midway through the sodium extraction in an operando coin cell, while the overall desodiation proceeds. The coincident emergence of the O2 structure reveals the rigid link between the local redox and the long-range order in this archetypal sodium-ion battery material. Structure-selective X-ray spectroscopy thus opens a powerful avenue for resolving the dynamic chemistry of different structural phases in multistructure electrochemical systems.
Cornell Chronicle Feature on Femtosecond control of phonon dynamics near a magnetic order critical point by Oleg in Nature Communications
The spin-phonon interaction in spin density wave (SDW) systems often determines the free energy landscape that drives the evolution of the system. When a passing energy flux, such as photoexcitation, drives a crystalline system far from equilibrium, the resulting lattice displacement generates transient vibrational states. Manipulating intermediate vibrational states in the vicinity of the critical point, where the SDW order parameter changes dramatically, would then allow dynamical control over functional properties. Here we combine double photoexcitation with an X-ray free-electron laser (XFEL) probe to control and detect the lifetime and magnitude of the intermediate vibrational state near the critical point of the SDW in chromium. We apply Landau theory to identify the mechanism of control as a repeated partial quench and sub picosecond recovery of the SDW. Our results showcase the capabilities to influence and monitor quantum states by combining multiple optical photoexcitations with an XFEL probe. They open new avenues for manipulating and researching the behaviour of photoexcited states in charge and spin order systems near the critical point.
New paper by Yifei is now published on Nano Letters and was featured by Cornell Chronicle and APS Science Highlights
All-solid-state lithium batteries promise significant improvements in energy density and safety over traditional liquid electrolyte batteries. The Al-doped Li7La3Zr2O12 (LLZO) solid-state electrolyte shows excellent potential given its high ionic conductivity and good thermal, chemical, and electrochemical stability. Nevertheless, further improvements on electrochemical and mechanical properties of LLZO call for an in-depth understanding of its local microstructure. Here, we employ Bragg coherent diffractive imaging to investigate the atomic displacements inside single grains of LLZO with various Al-doping concentrations, resulting in cubic, tetragonal, and cubic–tetragonal mixed structures. We observe coexisting domains of different crystallographic orientations in the tetragonal structure. We further show that Al doping leads to crystal defects such as dislocations and phase boundaries in the mixed- and cubic-phase grain. This study addresses the effect of Al doping on the nanoscale structure within individual grains of LLZO, which is informative for the future development of solid-state batteries.
Read the full paper here.
New paper on an algorithm for Bragg coherent x-ray diffractive imaging of highly strained nanocrystals by Ziyi and Oleg
By using phase retrieval, Bragg coherent diffractive imaging (BCDI) allows tracking of three-dimensional displacement fields inside individual nanocrystals. Nevertheless, during structural phase transformations, significant strains (1% and higher) are common, and BCDI fails due to the Bragg peak distortions. Here we present and advanced BCDI algorithm enabling imaging three-dimensional strain fields in highly strained crystals with separated structural phases. We test the algorithm on particles simulated to undergo a structural phase transformation. While the conventional algorithms fail in unambiguously reconstructing the phase morphology, our algorithm correctly retrieves the morphology of coexistent phases with a strain difference of 1%. The key novelty is the simultaneous reconstruction of multiple scans of the same nanoparticle at snapshots through the phase transformations. The algorithm enables visualizing phase transformations in nanoparticles of lithium-ion, sodium-ion nanoparticles, and other nanoparticulate materials in working conditions (operando).
Read the full paper here: DOI 10.1088/1367-2630/ab61db
This NSF CAREER award project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, seeks to understand degeneration in cathodes and find what makes a sodium-ion cathode material durable.
The award supports early-career faculty who have the potential to serve as academic role models in research and education and to lead advances in the mission of their department or organization. Research and activities pursued by early-career faculty build a firm foundation for a lifetime of leadership in integrating education and research. Over the next five years, Singer will receive over $700,000 to support his research.
Andrej Singer will lead a three-year project funded by the Department of Energy’s Office of Science that will attempt to create new quantum states of matter. Investigators include Darrell Schlom, the Herbert Fisk Johnson Professor of Industrial Chemistry; Kyle Shen, professor of physics; Nicole Benedek, assistant professor of materials science and engineering; and John Harter, Ph.D. ’13, assistant professor of materials at the University of California, Santa Barbara. The group will receive about $2.73 million from the DOE for its research.
Héctor Abruña, the Émile M. Chamot Professor in the Department of Chemistry and Chemical Biology and director of the Energy Materials Center at Cornell (EMC2), in collaboration with other faculty members, has been exploring electrocatalysis in alkaline (non-acidic) media, which could result in high-efficiency and high-performance fuel cells at a greatly reduced cost. Singer group is a member of the team.