Photoinduced Phase Transition Research Articles

All‐Optical Excitatory and Inhibitory Synapses Based on Reversible Photo‐Induced Phase Transition in Single‐Crystal CsPbBr3 Perovskite

AbstractThe hardware‐level construction of artificial synapses, mimicking the functionality of biological synapses, is widely acknowledged as a pivotal stride in artificial intelligence systems. Particularly, establishing all‐optical artificial synapses for neuromorphic computing, leveraging on‐chip optical interconnects instead of conventional wired connections, has garnered widespread attention. Here, high‐quality CsPbBr3 single crystals are synthesized, and intriguing relaxation processes associated with reversible photo‐induced phase transition (PIPT) are observed, leading to a corresponding change in the birefringence effect. The birefringence change is systematically analyzed by an optical system. The relaxation time of reversible PIPT is similar to the behavior patterns of biological synapses, enabling the device to mimic synaptic features. The device successfully mimics excitatory/inhibitory synaptic behaviors such as EPSP/IPSP, PPF, SDDP, SFDP, and SIDP by using 1310 nm signal. Furthermore, the device continues to exhibit excitatory/inhibitory synaptic functionality when 940 and 1550 nm signals are applied, achieving multi‐wavelength synaptic behaviors. The all‐optical devices have the advantages of low crosstalk, fast signaling, and wide optical bandwidth, which lays the foundation of all‐optical hardware for neuromorphic computing systems.

Photoinduced Electronic and Spin Topological Phase Transitions in Monolayer Bismuth.

Ultrathin bismuth exhibits rich physics including strong spin-orbit coupling, ferroelectricity, nontrivial topology, and light-induced structural dynamics. We use abinitio calculations to show that light can induce structural transitions to four transient phases in bismuth monolayers. These light-induced phases exhibit nontrivial topological character, which we illustrate using the recently introduced concept of spin bands and spin-resolved Wilson loops. Specifically, we find that the topology changes via the closing of the electron and spin band gaps during photoinduced structural phase transitions, leading to distinct edge states. Our study provides strategies to tailor electronic and spin topology via ultrafast control of photoexcited carriers and associated structural dynamics.

Ultrafast and persistent photoinduced phase transition at room temperature monitored by streaming powder diffraction

Ultrafast photoinduced phase transitions at room temperature, driven by a single laser shot and persisting long after stimuli, represent emerging routes for ultrafast control over materials’ properties. Time-resolved studies provide fundamental mechanistic insight into far-from-equilibrium electronic and structural dynamics. Here we study the photoinduced phase transformation of the Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98 material, designed to exhibit a 75 K wide thermal hysteresis around room temperature between MnIIIFeII tetragonal and MnIIFeIII cubic phases. We developed a specific powder sample streaming technique to monitor by ultrafast X-ray diffraction the structural and symmetry changes. We show that the photoinduced polarons expand the lattice, while the tetragonal-to-cubic photoinduced phase transition occurs within 100 ps above threshold fluence. These results are rationalized within the framework of the Landau theory of phase transition as an elastically-driven and cooperative process. We foresee broad applications of the streaming powder technique to study non-reversible and ultrafast dynamics.

Graphene‐Assisting Nonvolatile Vanadium Dioxide Phase Transition for Neuromorphic Machine Vision

AbstractAs a photoinduced and electro‐induced phase change material, VO2 undergoes a transition from an insulating phase to a metallic phase under photoelectric stimulation, accompanied by strong lattice distortion and band changes. This characteristic of simultaneously responding to optical and electrical signals provides a basis for simulating biological vision systems, but the volatility of phase transition challenges the Long‐term memory of neural networks. Here, a phase transition‐regulated artificial photoelectric synapse based on VO2/graphene heterostructure is proposed. Graphene serves as an electron exchange center, amplifying weak signals generated by VO2 phase transitions and achieving nonvolatile properties. Using the energy band change of VO2 before and after the photoinduced phase transition and the electron exchange with graphene, synaptic devices can be regulated by optical signals. The modulation of gate voltage on the Fermi level of graphene leads to the phase transition of VO2, thereby achieving the regulation of synapses by electrical signals. Extract the electrical conductivity difference between two equivalent synapses as synaptic weight values to train a three‐layer neural network. The trained neural network achieves high recognition accuracy and noise resistance for handwritten digits, which is of great significance for the application of artificial optoelectronic synapses in neural morphology calculation.

Non-negligible photostriction that accompanies the photoinduced phase transition process in VO<sub>2</sub>

<p>VO<sub>2</sub> experiences a transition from an insulating monoclinic phase to a metallic rutile phase near room temperature, which can be triggered by photoexcitation. This unique phenomenon highlights the significant potential of VO<sub>2</sub> in optoelectronic applications. However, the photoinduced shape deformation, also known as photostriction, which occurs during this phase transition has been largely overlooked. Here, we present findings on the photostriction of VO<sub>2</sub> ceramics and investigate the impact of photoinduced phase transition on its photostriction behavior. Large photostriction exceeding 0.1% is achievable in VO<sub>2</sub> ceramics when illuminated by both 405 and 655 nm monochromatic laser. In contrast to the majority of inorganic photostrictive materials, VO<sub>2</sub> demonstrates a nonlinear increase in photostriction as light intensity increases. Upon surpassing the threshold light intensity, the photo-triggered M-to-R phase transition leads to an anomalous increase, approximately 40%, in photostriction. Furthermore, the photoexcited structural evolution and the variation in photostrictive response to different light wavelengths are also depicted by ab initio molecular dynamics simulations. This study not only demonstrates VO<sub>2</sub> as an excellent inorganic material for photo-actuating applications, but also validates the effectiveness of utilizing photoinduced phase transition to explore high-performance inorganic photostrictive materials.</p>

Photoinduced topological phase transitions in Kitaev-Heisenberg honeycomb ferromagnets with the Dzyaloshinskii-Moriya interaction

We theoretically study topological properties of Floquet magnons in a laser-irradiated Kitaev-Heisenberg honeycomb ferromagnet with the Dzyaloshinskii-Moriya interaction by making use of the Floquet-Bloch theory. It is found that the Kitaev-Heisenberg honeycomb ferromagnet can reveal two topological phases with different Chern numbers when it is irradiated by the circular-polarized light. We find that the topological phase of the system can be switched from one topological phase to another one by adjusting the light intensity. The intrinsic Dzyaloshinskii-Moriya interaction plays a crucial role in the emergence of photoinduced topological phase transitions. It is shown that sign reversal of the thermal Hall conductivity is an important indicator on photoinduced topological phase transitions in the Kitaev-Heisenberg honeycomb ferromagnet.

Atomic-scale view of the photoinduced structural transition to form sp3-like bonded order phase in graphite

Photoexcitation of solids often induces structural phase transitions between different ordered phases, some of which are unprecedented and thermodynamically inaccessible. The phenomenon, known as photoinduced structural phase transition (PSPT), is of significant interest to the technological progress of advanced materials processing and the fundamental understanding of material physics. Here, we applied scanning tunnelling microscopy (STM) to directly characterise the primary processes of the PSPT in graphite to form a sp3-like carbon nano-phase called diaphite. The primary challenge was to provide microscopic views of the graphite-to-diaphite transition. On an atomic scale, STM imaging of the photoexcited surface revealed the nucleation and proliferation processes of the diaphite phase; these were governed by the formation of sp3-like interlayer bonds. The growth mode of the diaphite phase depends strongly on the photon energy of excitation laser light. Different dynamical pathways were proposed to explain the formation of a sp3-like interlayer bonding. Potential mechanisms for photon-energy-dependent growth were examined based on the experimental and calculated results. The present results provide insight towards realising optical control of sp2-to-sp3 conversions and the organisation of nanoscale structures in graphene-related materials.

Ultrafast dynamics of a photoinduced phase transition in single-crystal trititanium pentoxide

We investigate photoinduced phase transition of Ti3O5 using the pump-probe method in an ultrafast electron microscope. We measured time-resolved electron diffraction patterns of single-crystal lamellae of Ti3O5 excited by the femtosecond laser at the wavelength of 800 and 400 nm. Under 800 nm laser excitation, the photoinduced phase transition from the β-phase to the λ-phase with a similar timescale to previous measurements conducted using nanocrystals was observed. This indicates that the photoinduced phase transition is not a phenomenon influenced by the material surface, size, or boundary, but an intrinsic property in a bulk crystal of Ti3O5. The photoinduced phase transition was not detected, when excited by the laser at the wavelength of 400 nm. The results are discussed based on the electronic states of β-Ti3O5 and λ-Ti3O5. The density of the dissociated interatomic bonds between Ti at the specific site should be an important factor for triggering the photoinduced phase transition.

Following the Nonthermal Phase Transition in Niobium Dioxide by Time-Resolved Harmonic Spectroscopy.

Photoinduced phase transitions in correlated materials promise diverse applications from ultrafast switches to optoelectronics. Resolving those transitions and possible metastable phases temporally are key enablers for these applications, but challenge existing experimental approaches. Extreme nonlinear optics can help probe phase changes, as higher-order nonlinearities have higher sensitivity and temporal resolution to band structure and lattice deformations. Here the ultrafast transition from the semiconducting to the metallic phases in polycrystalline thin-film NbO_{2} is investigated by time-resolved harmonic spectroscopy. The emission strength of all harmonic orders shows a steplike suppression when the excitation fluence exceeds a threshold (∼11-12 mJ/cm^{2}), below the fluence required for the thermal transition-a signature of the nonthermal emergence of a metallic phase within 100±20 fs. This observation is backed by full abinitio simulations as well as a 1D chain model of high-harmonic generation from both phases. Our results demonstrate femtosecond harmonic probing of phase transitions and nonthermal dynamics in solids.

High-sensitivity extreme-ultraviolet transient absorption spectroscopy enabled by machine learning.

We present a novel denoising scheme for spectroscopy experiments employing broadband light sources and demonstrate its capabilities using transient absorption measurements with a high-harmonic source. Our scheme relies on measuring the probe spectra before and after interacting with the sample while capturing correlations between spectral components through machine learning approaches. With the present setup we achieve up to a tenfold improvement in noise suppression in XUV transient absorption spectra compared to the conventional pump on/ pump off referencing method. By utilizing strong spectral correlations in source fluctuations, the use of an artificial neural network facilitates pixel-wise noise reduction without requiring wavelength calibration of the reference spectrum. Our method can be adapted to a wide range of experiments and may be particularly advantageous for low repetition-rate systems, such as free electron lasers as well as laser-driven plasma and HHG sources. The enhanced sensitivity enables the investigation of subtle electron and lattice dynamics in the weak excitation regime, which is relevant for studying photovoltaics and photo-induced phase transitions in strongly correlated materials.

Light-Induced Nonthermal Phase Transition to the Topological Crystalline Insulator State in SnSe.

Femtosecond pulses have been used to reveal hidden broken symmetry states and induce transitions to metastable states. However, these states are mostly transient and disappear after laser removal. Photoinduced phase transitions toward crystalline metastable states with a change of topological order are rare and difficult to predict and realize experimentally. Here, by using constrained density functional perturbation theory and accounting for light-induced quantum anharmonicity, we show that ultrafast lasers can permanently transform the topologically trivial orthorhombic structure of SnSe into the topological crystalline insulating rocksalt phase via a first-order nonthermal phase transition. We describe the reaction path and evaluate the critical fluence and possible decay channels after photoexcitation. Our simulations of the photoexcited structural and vibrational properties are in excellent agreement with recent pump-probe data in the intermediate fluence regime below the transition with an error on the curvature of the quantum free energy of the photoexcited state that is smaller than 2%.

Capturing the non-equilibrium state in light–matter–free-electron interactions through ultrafast transmission electron microscopy

Ultrafast transmission electron microscope (UTEM) with the multimodality of time-resolved diffraction, imaging, and spectroscopy provides a unique platform to reveal the fundamental features associated with the interaction between free electrons and matter. In this review, we summarize the principles, instrumentation, and recent developments of the UTEM and its applications in capturing dynamic processes and non-equilibrium transient states. The combination of the transmission electron microscope with a femtosecond laser via the pump–probe method guarantees the high spatiotemporal resolution, allowing the investigation of the transient process in real, reciprocal and energy spaces. Ultrafast structural dynamics can be studied by diffraction and imaging methods, revealing the coherent acoustic phonon generation and photo-induced phase transition process. In the energy dimension, time-resolved electron energy-loss spectroscopy enables the examination of the intrinsic electronic dynamics of materials, while the photon-induced near-field electron microscopy extends the application of the UTEM to the imaging of optical near fields with high real-space resolution. It is noted that light–free-electron interactions have the ability to shape electron wave packets in both longitudinal and transverse directions, showing the potential application in the generation of attosecond electron pulses and vortex electron beams.

Observing femtosecond orbital dynamics in ultrafast Ge melting with time-resolved resonant X-ray scattering.

Photoinduced nonequilibrium phase transitions have stimulated interest in the dynamic interactions between electrons and crystalline ions, which have long been overlooked within the Born-Oppenheimer approximation. Ultrafast melting before lattice thermalization prompted researchers to revisit this issue to understand ultrafast photoinduced weakening of the crystal bonding. However, the absence of direct evidence demonstrating the role of orbital dynamics in lattice disorder leaves it elusive. By performing time-resolved resonant X-ray scattering with an X-ray free-electron laser, we directly monitored the ultrafast dynamics of bonding orbitals of Ge to drive photoinduced melting. Increased photoexcitation of bonding electrons amplifies the orbital disturbance to expedite the lattice disorder approaching the sub-picosecond scale of the nonthermal regime. The lattice disorder time shows strong nonlinear dependence on the laser fluence with a crossover behavior from thermal-driven to nonthermal-dominant kinetics, which is also verified by ab initio and two-temperature molecular dynamics simulations. This study elucidates the impact of bonding orbitals on lattice stability with a unifying interpretation on photoinduced melting.

Photoinduced Solid-Liquid Phase Transition and Energy Storage Enabled by the Design of Linked Double Photoswitches.

We demonstrate an effective design strategy of photoswitchable phase change materials based on the bis-azobenzene scaffold. These compounds display a solid phase in the E,E state and a liquid phase in the Z,Z state, in contrast to their monoazobenzene counterparts that exhibit less controlled phase transition behaviors that are largely influenced by their functional groups.

Photoinduced Ultrafast Phase Transition in Bilayer CrI3.

In two-dimensional magnets, the ultrafast photoexcited method represents a low-power and high-speed method of switching magnetic states. Bilayer CrI3 (BLC) is an ideal platform for studying ultrafast photoinduced magnetic phase transitions due to its stacking-dependent magnetic properties. Here, by using time-dependent density functional theory, we explore the photoexcitation phase transition in BLC from the R- to M-stacked phase. This process is found to be induced by electron-phonon interactions. The activated Ag and Bg phonon modes in the xy direction drive the horizontal relative displacements between the layers. The activated Ag mode in the z direction leads to a transition potential reduction. Furthermore, this phase transition can invert the sign of the interlayer spin interaction, indicating a photoinduced transition from ferromagnet to antiferromagnet. This investigation has profound implications for magnetic phase engineering strategies.

Neutral-to-ionic photoinduced phase transition of tetrathiafulvalene-p-chloranil by electronic and vibrational excitation: A real-time nuclear-electronic dynamics simulation study.

Tetrathiafulvalene-p-chloranil exhibits photoinduced phase transition (PIPT) between neutral (N) and ionic (I) phases, in which the constituent molecules are approximately charge-neutral and ionic, respectively. In addition to visible-light irradiation, which can induce both N → I and I → N PIPTs, infrared irradiation has been reported to induce the N → I PIPT. These results suggest that N → I and I → N PIPTs can be driven by electronic excitation, and the I → N PIPT can also be driven by vibrational excitation. However, the feasibility of the N → I PIPT using vibrational excitation remains an open question. In this study, we address this issue by simulating the PIPT processes using a nonadiabatic molecular dynamics approach combined with real-time electron dynamics at the level of a semiempirical quantum chemical model, density-functional tight binding. The results show the importance of vibronic interactions in the PIPT processes, thereby suggesting the possibility of N → I PIPT by vibrational excitations with infrared irradiation.

Photoinduced Phase Transition in Infinite-Layer Nickelates.

The quantum phase transition caused by regulating the electronic correlation in strongly correlated quantum materials has been a research hotspot in condensed matter science. Herein, a photon-induced quantum phase transition from the Kondo-Mott insulating state to the low temperature metallic one accompanying with the magnetoresistance changing from negative to positive in the infinite-layer NdNiO2 films is reported, where the antiferromagnetic coupling among the Ni1+ localized spins and the Kondo effect are effectively suppressed by manipulating the correlation of Ni-3d and Nd-5d electrons under the photoirradiation. Moreover, the critical temperature Tc of the superconducting-like transition exhibits a dome-shaped evolution with the maximum up to ≈42K, and the electrons dominate the transport process proved by the Hall effect measurements. These findings not only make the photoinduction a promising way to control the quantum phase transition by manipulating the electronic correlation in Mott-like insulators, but also shed some light on the possibility of the superconducting in electron-doped nickelates.

Optically Induced Multistage Phase Transition in Coherent Phonon-Dominated a-GeTe.

Ultrafast photoexcitation can decouple the multilevel nonequilibrium dynamics of electron-lattice interactions, providing an ideal probe for dissecting photoinduced phase transition in solids. Here, real-time time-dependent density functional theory simulations combined with occupation-constrained DFT methods are employed to explore the nonadiabatic paths of optically excited a-GeTe. Results show that the short-wavelength ultrafast laser is capable of generating full-domain carrier excitation and repopulation, whereas the long-wavelength ultrafast laser favors the excitation of lone pair electrons in the antibonded state. Photodoping makes the double-valley potential energy surface shallower and allows the insertion of A1g coherent forces in the atomic pairs, by which the phase reversal of Ge and Te atoms in the ⟨001⟩ direction is activated with ultrafast suppression of the Peierls distortion. These findings have far-reaching implications regarding nonequilibrium phase engineering strategies based on phase-change materials.

Inhomogeneous disordering at a photoinduced charge density wave transition

Symmetry-breaking phase transitions are ubiquitous in nature. The study of their dynamics in solids has often been performed using homogeneous order parameter theories. By microscopically modeling the photoinduced melting and recovery of a charge density wave, the authors instead show here that the transient dynamics can lead to disordered state, where the average order parameter is not representative of the atomic-scale configuration. This provides a possible minimal model description of the experimentally proposed inhomogeneous disordering pathway in photoinduced phase transitions.

Phase Transition‐Promoted Rapid Photomechanical Motions of Single Crystals of a Triene Coordination Polymer

AbstractMolecular crystals with the ability to transform light energy into macroscopic mechanical motions are a promising class of materials with potential applications in actuating and photonic devices. In regard to such materials, coordination polymers that exhibit dynamic photomechanical motion, associated with a phase transition, are unknown. Herein, we report an intriguing photoactive, one‐dimensional ZnII coordination polymer, 1, derived from 1,3,5‐tri‐4‐pyridyl‐1,2‐ethenylbenzene and 3,5‐difluorobenzoate. Single crystals of 1 under UV light irradiation exhibit rapid shrinking and bending, violent bursting‐jumping, splitting, and cracking behavior. Single‐crystal X‐ray diffraction analysis and 1H NMR spectroscopy reveal an unusual photoinduced phase transition involving a single‐crystal‐to‐single‐crystal [2+2] cycloaddition reaction that results in photomechanical responses. Interestingly, crystals of 1, which are triclinic with space group , are transformed into a higher symmetry, monoclinic cell with space group C2/c. This process represents a rare example of symmetry enhancement upon photoirradiation. The photomechanical activity is likely due to the sudden release of stress associated with strained molecular geometries and significant solid‐state molecular movement arising from cleavage and formation of chemical bonds. A composite membrane fabricated from 1 and polyvinyl alcohol (PVA) also displays interesting photomechanical behavior under UV light illumination, indicating the material's potential as a photoactuator.