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Transient absorption (TA) spectroscopy is considered as a powerful technique that reflects the ultrafast dynamics of photogenerated carriers in photoelectric and photocatalysis materials. However, limited by its sensitivity, the photogenerated carrier density in TA measurements of solar energy materials is usually much higher than that in the real working condition. Here, we present a combination of kHz macro-pulse and MHz micro-pulse technique for an ultrahigh sensitive TA spectrometer, which improves the sensitivity to the 10−7 level of ΔOD. It enables us to study ultrafast carrier dynamics pumped by very low power, which can avoid the influence of many-body interactions and the nonlinear effect associated with high carrier density. This work provides a novel TA method with ultrahigh sensitivity, which will play an important role in investigating the carrier dynamics of semiconductors in the working condition.

We demonstrate a method to synthesize ultra-high repetition rate bursts of ultrashort laser pulses containing any number of pulses within a burst with identical pulse separation and adjustable amplitude. The key element to synthesize the GHz bursts of ultrashort laser pulses is an active fiber loop. The method was implemented in the fiber chirped pulse amplification system to obtain 72 nJ-energy bursts of 20 pulses with a 2.65 GHz intra-burst pulse repetition rate and a 500 kHz burst repetition rate. The dispersion compensation mechanism ensured a mean pulse duration of 570 fs within the bursts.

Rope-like structures are ubiquitous in Nature. They are supermolecular assemblies of macromolecules responsible for the structural and mechanical integrity of plant and animal tissues. Collagen fibrils with diameters between 50 and 500 nm and their helical supermolecular structure are good examples of such nanoscale biological ropes. Like man-made laid ropes, fibrils are typically loaded in tension, and due to their large aspect ratio, they are, in principle, prone to buckling and torsional instabilities. One way to study buckling of a rigid rod is to attach it to a stretched elastic substrate that is then returned to its original length. In the case of single collagen fibrils, the observed behavior depends on the degree of hydration. By going from buckling in ambient conditions to immersed in a buffer, fibrils go from the well-known sine wave response to a localized behavior reminiscent of the bird-caging of laid ropes. In addition, in ambient conditions, the sine wave response coexists with the formation of loops along the length of the fibrils, as observed for the torsional instability of a twisted filament when tension is decreased. This work provides direct evidence that single collagen fibrils are highly susceptible to axial compression because of their helical supermolecular structure. As a result, mammals that use collagen fibrils as their main load-bearing element in many tissues have evolved mitigating strategies that protect single fibrils from axial compression damage.

It is well known that dielectric breakdown in a liquid generates cavitation bubbles and shock waves. Here we demonstrate that when the liquid is bounded by two solid glass boundaries (10–20-μm separation), rings of microscopic bubbles can be nucleated around the laser-induced cavitation bubble. While generally acoustic nucleation is achieved with longitudinal waves of sufficient tension, this work demonstrates that acoustic cavitation can also be generated from transverse waves. Our experiments identify three waves originating at the boundaries: the fastest is the bulk wave in the solid, followed by a leaky Rayleigh wave at the liquid-solid contact, which is trailed by a Lamb-type wave. For the latter, the two solid boundaries act as a wave guide and generate intense and short-lived cavitation activity within the gap. Streak photography and high-speed photography reveal the microsecond-duration cavitation-bubble dynamics, and subpicosecond strobe photography visualizes the mechanism of bubble nucleation from the accelerated surface. Simulations coupling the solid mechanics with the acoustics support the experimentally observed mechanisms of transverse-wave-induced cavitation inception.

Al-doped ZnO (AZO) thin films were deposited on p-Si (100) by pulsed laser deposition from a composite ceramic target (ZnO:Al₂O₃) by using 355 nm laser at different O₂ background pressure and substrate temperature. Upon ablation at laser fluence of 2 Jcm⁻², plasma plume consists of Zn neutrals and ions, Al neutrals and O neutral are formed. As the O₂ background pressure increases from 3 Pa to 26 Pa, the energy of the plasma species are moderated. The results show that the ions density and velocity reduced significantly above 13 Pa. The velocity of the ions reduced from 14 kms⁻¹ to 11 kms⁻¹ at 13 Pa, while the ions energy reduced from 63 eV to 42 eV respectively. Below 13 Pa, crystalline and homogeneous AZO nanostructured films were formed. Above 13 Pa, the process results in low crystallinity films with higher porosity. The resistivity of the films also increases from 0.1 ohmcm to 24 ohmcm as the pressure increased. At fixed O₂ background pressure of 3 Pa, the adatom mobility of atoms on the substrates is altered by substrate heating. The resistivity of the films decreased to 10^–3 ohmcm when the substrates are heated to 100 °C–300 °C during deposition. The films with highest carrier density of 10²⁰ cm⁻³ and carrier mobility of 13 cmV⁻¹ s⁻¹ are achieved at 200 °C.

FemtoLux 3 laser was used as an illumination source in the wide-field second harmonic generation (SHG) microscope. Relatively high laser pulse energy at a medium pulse repetition frequency allowed for a faster single image acquisition compared to that using laser-scanning. It was also possible to acquire images of relatively large sample areas, which paved the way for the rapid imaging of macroscopic sample areas with microscopic resolution.

Hydrogen bonding interactions play an important role in many chemical and physical processes occurring in bulk liquids and at interfaces. In this study, hydrous species (H₂O and Si-OH) on nano-porous alteration layers (gels) formed on a boroaluminosilicate glass called International Simple Glass corroded in aqueous solutions at pH 7 and pH 9, and initially saturated with soluble silicon-containing species were analyzed using linear and non-linear vibrational spectroscopy in combination with molecular dynamics simulations. The simulation results revealed various possible types of hydrogen bonds among these hydrous species in nanoconfinement environments with their populations depending on pore-size distribution. The nano-porous gels formed on corroded glass surfaces enhance hydrogen bond strength between hydrous species as revealed by attenuated total reflectance infrared spectroscopy. Sum frequency generation spectroscopy showed some significant differences in hydrogen bonding interactions on alteration layers formed at pH 7 and pH 9. The glass dissolution under the leaching conditions used in this study has been known to be ten times faster at pH 7 in comparison to that at pH 9 due to unknown reasons. The simulation and experimental results obtained in this study indicate that the water mobility in the gel formed at pH 9 could be slower than that in the gel formed at pH 7, and as a result, the leaching rate at pH 9 is slower than that at pH 7.

We investigate anionic [Co,CO₂,nH₂O]⁻ clusters as model systems for the electrochemical activation of CO₂ by infrared multiple photon dissociation (IRMPD) spectroscopy in the range of 1250–2234 cm⁻¹ using an FT-ICR mass spectrometer. We show that both CO₂ and H₂O are activated in a significant fraction of the [Co,CO₂,H₂O]⁻ clusters since it dissociates by CO loss, and the IR spectrum exhibits the characteristic C−O stretching frequency. About 25 % of the ion population can be dissociated by pumping the C−O stretching mode. With the help of quantum chemical calculations, we assign the structure of this ion as Co(CO)(OH)₂⁻. However, calculations find Co(HCOO)(OH)⁻ as the global minimum, which is stable against IRMPD under the conditions of our experiment. Weak features around 1590–1730 cm⁻¹ are most likely due to higher lying isomers of the composition Co(HOCO)(OH)⁻. Upon additional hydration, all species [Co,CO₂,nH₂O]⁻, n≥2, undergo IRMPD through loss of H₂O molecules as a relatively weakly bound messenger. The main spectral features are the C−O stretching mode of the CO ligand around 1900 cm⁻¹, the water bending mode mixed with the antisymmetric C−O stretching mode of the HCOO⁻ ligand around 1580–1730 cm⁻¹, and the symmetric C−O stretching mode of the HCOO⁻ ligand around 1300 cm⁻¹. A weak feature above 2000 cm⁻¹ is assigned to water combination bands. The spectral assignment clearly indicates the presence of at least two distinct isomers for n ≥2.

The generation, control and transfer of triplet excitons in molecular and hybrid systems is of great interest owing to their long lifetime and diffusion length in both solid-state and solution phase systems, and to their applications in light emission1, optoelectronics, photon frequency conversion and photocatalysis. Molecular triplet excitons (bound electron–hole pairs) are ‘dark states’ because of the forbidden nature of the direct optical transition between the spin-zero ground state and the spin-one triplet levels. Hence, triplet dynamics are conventionally controlled through heavy-metal-based spin–orbit coupling or tuning of the singlet–triplet energy splitting via molecular design. Both these methods place constraints on the range of properties that can be modified and the molecular structures that can be used. Here we demonstrate that it is possible to control triplet dynamics by coupling organic molecules to lanthanide-doped inorganic insulating nanoparticles. This allows the classically forbidden transitions from the ground-state singlet to excited-state triplets to gain oscillator strength, enabling triplets to be directly generated on molecules via photon absorption. Photogenerated singlet excitons can be converted to triplet excitons on sub-10-picosecond timescales with unity efficiency by intersystem crossing. Triplet exciton states of the molecules can undergo energy transfer to the lanthanide ions with unity efficiency, which allows us to achieve luminescent harvesting of the dark triplet excitons. Furthermore, we demonstrate that the triplet excitons generated in the lanthanide nanoparticle–molecule hybrid systems by near-infrared photoexcitation can undergo efficient upconversion via a lanthanide–triplet excitation fusion process: this process enables endothermic upconversion and allows efficient upconversion from near-infrared to visible frequencies in the solid state. These results provide a new way to control triplet excitons, which is essential for many fields of optoelectronic and biomedical research.

Photolabile chelating cages or protecting groups need complex chemical syntheses and require UV, visible, or two-photon NIR light to trigger release. Different cages have different solubilities, reaction rates, and energies required for triggering. Here we show that liposomes containing calcium, adenosine triphosphate, or carboxyfluorescein are tethered to plasmon-resonant hollow gold nanoshells (HGN) tuned to absorb light from 650–950 nm. Picosecond pulses of near infrared (NIR) light provided by a two-photon microscope, or by a stand-alone laser during flow through microfluidic channels, trigger contents release with spatial and temporal control. NIR light adsorption heats the HGN, inducing vapor nanobubbles that rupture the liposome, releasing cargo within milliseconds. Any water-soluble molecule can be released at essentially the same rate from the liposome-HGN. By using liposomes of different composition, or HGN of different sizes or shapes with different nanobubble threshold fluences, or irradiating on or off resonance, two different cargoes can be released simultaneously, one before the other, or in a desired ratio. Calcium release from liposome-HGN can be spatially patterned to crosslink alginate gels and trap living cells. Liposome-HGN provide stable, biocompatible isolation of the bioactive compound from its surroundings with minimal interactions with the local environment.