During femtosecond laser fabrication, photons are mainly absorbed by electrons, and the subsequent energy transfer from electrons to ions is of picosecond order. Hence, lattice motion is negligible within the femtosecond pulse duration, whereas femtosecond photon-electron interactions dominate the entire fabrication process. Therefore, femtosecond laser fabrication must be improved by controlling localized transient electron dynamics, which poses a challenge for measuring and controlling at the electron level during fabrication processes. Pump-probe spectroscopy presents a viable solution, which can be used to observe electron dynamics during a chemical reaction. In fact, femtosecond pulse durations are shorter than many physical/chemical characteristic times, which permits manipulating, adjusting, or interfering with electron dynamics. Hence, we proposed to control localized transient electron dynamics by temporally or spatially shaping femtosecond pulses, and further to modify localized transient materials properties, and then to adjust material phase change, and eventually to implement a novel fabrication method. This review covers our progresses over the past decade regarding electrons dynamics control (EDC) by shaping femtosecond laser pulses in micro/nanomanufacturing: (1) Theoretical models were developed to prove EDC feasibility and reveal its mechanisms; (2) on the basis of the theoretical predictions, many experiments are conducted to validate our EDC-based femtosecond laser fabrication method. Seven examples are reported, which proves that the proposed method can significantly improve fabrication precision, quality, throughput and repeatability and effectively control micro/nanoscale structures; (3) a multiscale measurement system was proposed and developed to study the fundamentals of EDC from the femtosecond scale to the nanosecond scale and to the millisecond scale; and (4) As an example of practical applications, our method was employed to fabricate some key structures in one of the 16 Chinese National S&T Major Projects, for which electron dynamics were measured using our multiscale measurement system.

Zero-dimensional MoS₂ quantum dots (QDs) possess distinct physical and chemical properties, which have garnered them considerable attention and facilitates their use in a broad range of applications. In this study, we prepared monolayer MoS₂ QDs using temporally shaped femtosecond laser ablation of bulk MoS₂ targets in water. The morphology, crystal structures, chemical, and optical properties of the MoS₂ QDs were characterized by transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, UV–vis absorption spectra, and photoluminescence spectra. The analysis results show that highly pure, uniform, and monolayer MoS₂ QDs can be successfully prepared. Moreover, by temporally shaping a conventional single pulse into a two-subpulse train, the production rate of MoS₂ nanomaterials (including nanosheets, nanoparticles, and QDs) and the ratio of small size MoS₂ QDs can be substantially improved. The underlying mechanism is a combination of multilevel photoexfoliation of monolayer MoS₂ and water photoionization–enhanced light absorption. The as-prepared MoS₂ QDs exhibit excellent electrocatalytic activity for hydrogen evolution reactions because of the abundant active edge sites, high specific surface area, and excellent electrical conductivity. Thus, this study provides a simple and green alternative strategy for the preparation of monolayer QDs of transition metal dichalcogenides or other layered materials.

We proposed combining temporally shaped (double-pulse train) laser pulses with spatially shaped (Bessel beam) laser pulses. By using a temporally shaped femtosecond laser Bessel-beam-assisted chemical etching method, the energy deposition efficiency was improved by adjusting the pulse delay to yield a stronger material modification and, thus, a higher etching depth. The etching depth was enhanced by a factor of 13 using the temporally shaped Bessel beam. The mechanism of etching depth enhancement was elucidated by localized transient-free electrons dynamics-induced structural and morphological changes. Micro-Raman spectroscopy was conducted to verify the structural changes inside the material. This method enables high-throughput, high-aspect-ratio microchannel fabrication in fused silica for potential applications in microfluidics.

Ultratrace molecular detections from a limited amount of highly diluted solutions can offer unprecedented benefits in the biomedical/analytical fields, such as in precancer diagnosis, forensic analysis, and food safety. However, huge difficulties exist in completely concentrating the target molecules within a sensitive area and thereby enhancing the detection sensitivity. Herein, we report the ultratrace molecular detection using a low-adhesive superhydrophobic surface-enhanced Raman spectroscopy (LAS-SERS) substrate fabricated by femtosecond laser ablation. The LAS-SERS substrate has good characteristics, including a contact angle as high as 154°, a contact angle hysteresis below 5°, and a simulated Raman signal enhancement factor of up to 6 × 10⁶. Compared to the previously developed superhydrophobic SERS (S-SERS) methods, the low-adhesive nature of the LAS-SERS method can greatly reduce the final contact area, thus significantly enhancing the detection limit. In our experiments, the final contact area of the LAS-SERS substrate was reduced by 19.5 times, corresponding to an 88.1 times increase in the concentration effect, as compared to the highly adhesive S-SERS substrates fabricated using the same technique. The enhanced condensation effect led to a detection limit as low as 10⁻¹⁴ M, which shows an obvious improvement compared to that of the other non-photolithography methods. The method reported herein offers a facile and efficient approach to the cost-effective fabrication of a high-performance LAS-SERS substrate for ultratrace molecular detection.