Femtosecond Pump-probe Microscopy Research Articles

Imaging Ultrafast Dynamics of Pressure-Driven Phase Transitions in Black Phosphorus and Anomalous Coherent Phonon Softening.

Applying high pressure to effectively modulate the electronic and lattice structures of materials could unravel various physical properties associated with phase transitions. In this work, high-pressure-compatible femtosecond pump-probe microscopy was constructed to study the pressure-dependent ultrafast dynamics in black phosphorus (BP) thin films. We observed pressure-driven evolution of the electronic topological transition and three structural phases as the pressure reached ∼22 GPa, which could be clearly differentiated in the transient absorption images containing spatially resolved ultrafast carrier and coherent phonon dynamics. Surprisingly, an anomalous coherent acoustic phonon mode with pressure softening behavior was observed within the range of ∼3-8 GPa, showing distinct laser power and time dependences. Density functional theory calculations show that this mode, identified as the shear mode along the armchair orientation, gains significant electron-phonon coupling strength from out-of-plane compression that leads to decreased phonon frequency. Our results provide insights into the structure evolution of BP with pressure and hold potential for applications in microelectromechanical devices.

Nondestructive Nonlinear Optical Microscopy Revealed the Blackening Mechanism of Ancient Chinese Jades.

Jade is most valued in Chinese culture since ancient times. For unearthed jade artifacts, the alteration color resulting from weathering effects and human activities provides information for cultural heritage conservation, archaeology, and history. Currently, the noninvasive 3-dimensional characterization of jade artifacts with high chemical and spatial resolution remains challenging. In this work, we applied femtosecond pump-probe microscopy and second harmonic generation microscopy techniques to study the black alteration of an ancient jade artifact of the late Spring and Autumn period (546 to 476 BC). The direct cause of the "mercury alteration" phenomena was discovered to be the conversion of metacinnabar from buried cinnabar in the tomb. Furthermore, a 3-dimensional optical reconstruction of the black alteration was achieved, providing a high-resolution method for analyzing the blackening mechanism without the need of sample damage. Our approach opens up new opportunities to extract microscopic spatiochemical information for a broad range of alteration colors in jade artifacts.

Charge-transfer biexciton annihilation in a donor-acceptor co-crystal yields high-energy long-lived charge carriers.

Organic donor–acceptor (D–A) co-crystals have attracted much interest due to their important optical and electronic properties. Co-crystals having ⋯DADA⋯ π-stacked morphologies are especially interesting because photoexcitation produces a charge-transfer (CT) exciton, D˙+–A˙−, between adjacent D–A molecules. Although several studies have reported on the steady-state optical properties of this type of CT exciton, very few have measured the dynamics of its formation and decay in a single D–A co-crystal. We have co-crystallized a peri-xanthenoxanthene (PXX) donor with a N,N-bis(3-pentyl)-2,5,8,11-tetraphenylperylene-3,4:9,10-bis(dicarboximide) (Ph4PDI) acceptor to give an orthorhombic PXX–Ph4PDI ⋯DADA⋯ π-stacked co-crystal with a CT transition dipole moment that is perpendicular to the transition moments for Sn ← S0 excitation of PXX and Ph4PDI. Using polarized, broadband, femtosecond pump–probe microscopy, we have determined that selective photoexcitation of Ph4PDI in the single co-crystal results in CT exciton formation within the 300 fs instrument response time. At early times (0.3 ≤ t ≤ 500 ps), the CT excitons decay with a t−1/2 dependence, which is attributed to CT biexciton annihilation within the one-dimensional ⋯DADA⋯ π-stacks producing high-energy, long-lived (>8 ns) electron–hole pairs in the crystal. These energetic charge carriers may prove useful in applications ranging from photovoltaics and opto-electronics to photocatalysis.

Pump-probe microscopy of femtosecond laser ablation in air and liquids

The ablation process of femtosecond laser pulses of iron in air and different liquids was investigated for fluences of 0.5 J/cm2 and 2 J/cm2 by means of femtosecond pump-probe microscopy. Measurements of the relative change in reflectivity suggest that the surrounding liquid has a significant impact on the ablation process. During the heating phase of the metal within the first picoseconds after laser beam impact, the change in reflectivity in air and liquids is similar. Afterwards, the vapor and melt expulsion in air leads to a strong decrease in reflectivity, while the change in reflectivity in the liquids shows a more complex fluence and time-dependent behavior. This behavior is suggested to be triggered by the expansion of the molten surface and chemical reactions on the picosecond timescale.

Label-free imaging of hemoglobin degradation and hemosiderin formation in brain tissues with femtosecond pump-probe microscopy.

The degradation of hemoglobin in brain tissues results in the deposition of hemosiderin, which is a major form of iron-storage protein and closely related to neurological disorders such as epilepsy. Optical detection of hemosiderin is vitally important yet challenging for the understanding of disease mechanisms, as well as improving surgical resection of brain lesions. Here, we provide the first label-free microscopy study of sensitive hemosiderin detection in both an animal model and human brain tissues.Methods: We applied spectrally and temporally resolved femtosecond pump-probe microscopy, including transient absorption (TA) and stimulated Raman scattering (SRS) techniques, to differentiate hemoglobin and hemosiderin in brain tissues. The label-free imaging results were compared with Perls' staining to evaluate our method for hemosiderin detection.Results: Significant differences between hemoglobin and hemosiderin transient spectra were discovered. While a strong ground-state bleaching feature of hemoglobin appears in the near-infrared region, hemosiderin demonstrates pure excited-state absorption dynamics, which could be explained by our proposed kinetic model. Furthermore, simultaneous imaging of hemoglobin and hemosiderin can be rapidly achieved in both an intracerebral hemorrhage (ICH) rat model and human brain surgical specimens, with perfect correlation with Perls' staining.Conclusion: Our results suggest that rapid, label-free detection of hemosiderin in brain tissues could be realized by femtosecond pump-probe microscopy. Our method holds great potential in providing a new tool for intraoperative detection of hemosiderin during brain surgeries.

Inhomogeneity of the ultrafast insulator-to-metal transition dynamics of VO2

The insulator-to-metal transition (IMT) of the simple binary compound of vanadium dioxide VO$_2$ at $\sim 340$ K has been puzzling since its discovery more than five decades ago. A wide variety of photon and electron probes have been applied in search of a satisfactory microscopic mechanistic explanation. However, many of the conclusions drawn have implicitly assumed a {\em homogeneous} material response. Here, we reveal inherently {\em inhomogeneous} behavior in the study of the dynamics of individual VO$_2$ micro-crystals using a combination of femtosecond pump-probe microscopy with nano-IR imaging. The time scales of the photoinduced bandgap reorganization in the ultrafast IMT vary from $\simeq 40 \pm 8$ fs, i.e., shorter than a suggested phonon bottleneck, to $\sim 200\pm20$ fs, with an average value of $80 \pm 25$ fs, similar to results from previous studies on polycrystalline thin films. The variation is uncorrelated with crystal size, orientation, transition temperature, and initial insulating phase. This together with details of the nano-domain behavior during the thermally-induced IMT suggests a significant sensitivity to local variations in, e.g., doping, defects, and strain of the microcrystals. The combination of results points to an electronic mechanism dominating the photoinduced IMT in VO$_2$, but also highlights the difficulty of deducing mechanistic information where the intrinsic response in correlated matter may not yet have been reached.

Reversible strain-induced electron-hole recombination in silicon nanowires observed with femtosecond pump-probe microscopy.

Strain-induced changes to the electronic structure of nanoscale materials provide a promising avenue for expanding the optoelectronic functionality of semiconductor nanostructures in device applications. Here we use pump-probe microscopy with femtosecond temporal resolution and submicron spatial resolution to characterize charge-carrier recombination and transport dynamics in silicon nanowires (NWs) locally strained by bending deformation. The electron-hole recombination rate increases with strain for values above a threshold of ∼1% and, in highly strained (∼5%) regions of the NW, increases 6-fold. The changes in recombination rate are independent of NW diameter and reversible upon reduction of the applied strain, indicating the effect originates from alterations to the NW bulk electronic structure rather than introduction of defects. The results highlight the strong relationship between strain, electronic structure, and charge-carrier dynamics in low-dimensional semiconductor systems, and we anticipate the results will assist the development of strain-enabled optoelectronic devices with indirect-bandgap materials such as silicon.

Femtosecond pump-probe microscopy generates virtual cross-sections in historic artwork

The layering structure of a painting contains a wealth of information about the artist's choice of materials and working methods, but currently, no 3D noninvasive method exists to replace the taking of small paint samples in the study of the stratigraphy. Here, we adapt femtosecond pump-probe imaging, previously shown in tissue, to the case of the color palette in paintings, where chromophores have much greater variety. We show that combining the contrasts of multispectral and multidelay pump-probe spectroscopy permits nondestructive 3D imaging of paintings with molecular and structural contrast, even for pigments with linear absorption spectra that are broad and relatively featureless. We show virtual cross-sectioning capabilities in mockup paintings, with pigment separation and nondestructive imaging on an intact 14th century painting (The crucifixion by Puccio Capanna). Our approach makes it possible to extract microscopic information for a broad range of applications to cultural heritage.

Pump–Probe Microscopy: Spatially Resolved Carrier Dynamics in ZnO Rods and the Influence of Optical Cavity Resonator Modes

Femtosecond pump-probe microscopy is used to investigate the charge recombination dynamics at different points within a single needle-shaped ZnO rod. Recombination in the tips of the rod occurs through an excitonic or electron-hole plasma state, taking place on a picosecond time scale. Photoexcitation in the larger diameter sections of the interior exhibit dramatically slower recombination that occurs primarily through defects sites, i.e., trap mediated recombination. Transient absorption imaging shows that the spatial variation in the dynamics is also influenced by the cavity resonances supported within the hexagonal cross section of the rod. Finite element simulations suggest that these optical resonator modes produce qualitatively different intensity patterns in the two different locations. Near the end of the rod, the intensity pattern has significant standing-wave character, which leads to the creation of photoexcited carriers in the core of the structure. The larger diameter regions, on the other hand, exhibit intensity distributions in which the whispering gallery (WG) mode character dominates. At these locations, the photoexcited carriers are produced in subsurface depletion zone, where the internal fields separate the electrons and holes and lead to a greater degree of trap recombination on longer time scales.

The End Is Different than The Middle: Spatially Dependent Dynamics in ZnO Rods Observed by Femtosecond Pump–Probe Microscopy

Pump–probe transient absorption microscopy was used to follow the electron–hole (e–h) recombination dynamics at different points within individual needle-shaped ZnO rods to characterize spatial dif...