Directly Unveiling the Energy Transfer Dynamics between Alq3 Molecules and Si by Ultrafast Optical Pump-Probe Spectroscopy.

The energy transfer (ET) between organic molecules and semiconductors is a crucial mechanism for enhancing the performance of semiconductor-based optoelectronic devices, but it remains undiscovered. Here, ultrafast optical pump-probe spectroscopy was utilized to directly reveal the ET between organic Alq3 molecules and Si semiconductors. Ultrathin SiO2 dielectric layers with a thickness of 3.2-10.8 nm were inserted between Alq3 and Si to prevent charge transfer. By means of the ET from Alq3 to Si, the SiO2 thickness-dependent relaxation dynamics of photoexcited carriers in Si have been unambiguously observed on the transient reflectivity change (ΔR/R) spectra, especially for the relaxation process on a time scale of 200-350 ps. In addition, these findings also agree with the results of our calculation in a model of long-range dipole-dipole interactions, which provides critical information for developing future optoelectronic devices.

Few-cycle THz wave manipulation with a high degree of freedom via f-t modulation.

THz waves have been intensively applied in many fields, e.g., spectroscopy, imaging, and communications. However, owing to the rarity of available techniques for manipulating circularly polarized few-cycle THz waves on picosecond time scales, most of the current studies are conducted with linearly polarized THz waves. Here we demonstrate circularly polarized (CP) THz (dual) pulses generated by a polarization-twisting pulse/dual pulse (PTP/PTDP). The polarization-twisting optical dual pulses can be generated via a modified Michelson interferometer (MI) system, which provides the ability to control the frequency, helicity, and time interval of the dual pulses arbitrarily and individually. Such a novel, to the best of our knowledge, modulation technique shows huge potential for applications, not only in imaging and spectroscopy but also in next-generation communications.

Investigation of TiO2 nanoparticle interactions in the fibroblast NIH-3T3 cells via liquid-mode atomic force microscope.

Long before we recognized how significant they were, nanoparticles were already all around in the environment. Since then, an extensive number of synthetic nanoparticles have been engineered to improve our quality of life through rigorous scientific research on their uses in practically every industry, including semiconductor devices, food, medicine, and agriculture. The extensive usage of nanoparticles in commodities that come into proximity with human skin and internal organs through medicine has raised significant concerns over the years. TiO2 nanoparticles (NPs) are widely employed in a wide range of industries, such as cosmetics and food packaging. The interaction and internalization of TiO2 NPs in living cells have been studied by the scientific community for many years. In the present study, we investigated the cell viability, nanomechanical characteristics, and fluorescence response of NIH-3T3 cells treated with sterile DMEM TiO2 nanoparticle solution using a liquid-mode atomic force microscope and a fluorescence microscope. Two different sorts of response systems have been observed in the cells depending on the size of the NPs. TiO2 nanoparticles smaller than 100 nm support its initial stages cell viability, and cells internalize and metabolize NPs. In contrast, bigger TiO2 NPs (> 100 nm) are not completely metabolized and cannot impair cell survival. Furthermore, bigger NPs above 100 nm could not be digested by the cells, therefore hindering cell development, whereas below 100 nm TiO2 stimulated uncontrolled cell growth akin to cancerous type cells. The cytoskeleton softens as a result of particle internalization, as seen by the nanomechanical characteristics of the nanoparticle treated cells. According to our investigations, TiO2 smaller than 100 nm facilitates unintended cancer cell proliferation, whereas larger NPs ultimately suppress cell growth. Before being incorporated into commercial products, similar effects or repercussions that could result from employing different NPs should be carefully examined.

Spin-Polarized Photocatalytic CO2 Reduction of Mn-Doped Perovskite Nanoplates.

"Spin" has been recently reported as an important degree of electronic freedom to improve the performance of electrocatalysts and photocatalysts. This work demonstrates the manipulations of spin-polarized electrons in CsPbBr3 halide perovskite nanoplates (NPLs) to boost the photocatalytic CO2 reduction reaction (CO2RR) efficiencies by doping manganese cations (Mn2+) and applying an external magnetic field. Mn-doped CsPbBr3 (Mn-CsPbBr3) NPLs exhibit an outstanding photocatalytic CO2RR compared to pristine CsPbBr3 NPLs due to creating spin-polarized electrons after Mn doping. Notably, the photocatalytic CO2RR of Mn-CsPbBr3 NPLs is significantly enhanced by applying an external magnetic field. Mn-CsPbBr3 NPLs exhibit 5.7 times improved performance of photocatalytic CO2RR under a magnetic field of 300 mT with a permanent magnet compared to pristine CsPbBr3 NPLs. The corresponding mechanism is systematically investigated by magnetic circular dichroism spectroscopy, ultrafast transient absorption spectroscopy, and density functional theory simulation. The origin of enhanced photocatalytic CO2RR efficiencies of Mn-CsPbBr3 NPLs is due to the increased number of spin-polarized photoexcited carriers by synergistic doping of the magnetic elements and applying a magnetic field, resulting in prolonged carrier lifetime and suppressed charge recombination. Our result shows that manipulating spin-polarized electrons in photocatalytic semiconductors provides an effective strategy to boost photocatalytic CO2RR efficiencies.

Stabilized High-Membered and Phase-Pure 2D All Inorganic Ruddlesden-Popper Halide Perovskites Nanocrystals as Photocatalysts for the CO2 Reduction Reaction.

In contrast to the 2D organic-inorganic hybrid Ruddlesden-Popper halide perovskites (RPP), a new class of 2D all inorganic RPP (IRPP) has been recently proposed by substituting the organic spacers with an optimal inorganic alternative of cesium cations (Cs+ ). Nevertheless, the synthesis of high-membered 2D IRPPs (n > 1) has been a very challenging task because the Cs+ need to act as both spacers and A-site cations simultaneously. This work presents the successful synthesis of stable phase-pure high-membered 2D IRPPs of Csn+1 Pbn Br3n+1 nanosheets (NSs) with n = 3 and 4 by employing the strategy of using additional strong binding bidentate ligands. The structures of the 2D IRPPs (n = 3 and 4) NSs are confirmed by powder X-ray diffraction and high-resolution aberration-corrected scanning transmission electron microscope measurements. These 2D IRPPs NSs exhibit a strong quantum confinement effect with tunable absorption and emission in the visible light range by varying their n values, attributed to their inherent 2D quantum-well structure. The superior structural and optical stability of the phase-pure high-membered 2D IRPPs make them a promising candidate as photocatalysts in CO2 reduction reactions with outstanding photocatalytic performance and long-term stability.

Generation of sub-half-cycle 10 µm pulses through filamentation at kilohertz repetition rates.

We have experimentally demonstrated the generation of sub-half-cycle phase-stable pulses with the carrier wavelength of 10.2 µm through two-color filamentation in nitrogen. The carrier-envelope phase (CEP) of the MIR pulse is passively stabilized and controlled by the attosecond time delay between the two-color input pulses. The duration of the MIR pulse is 13.7 fs, which corresponds to 0.402 cycles. The absolute value of the CEP of the generated sub-half-cycle pulse is consistent with a simple four-wave difference frequency generation model. We have also found that the 10 kHz repetition rate of the light source causes the fluctuation of the pulse energy on a few hundred millisecond time scale.

Selenium nanoparticle prepared by femtosecond laser-induced plasma shock wave.

A novel approach for the production of both amorphous and crystalline selenium nanoparticles (SeNPs) using femtosecond laser-induced plasma shock wave on the surface of Bi2Se3 topological insulators at room temperature and ambient pressure is demonstrated. The shape and size of SeNPs can be reliably controlled via the kinetic energy obtained from laser pulses, so these are applicable as active components in nanoscale applications. Importantly, the rapid, low-cost and eco-friendly synthesis strategy developed in this study could also be extendable to other systems.

Generation and manipulation of polarization-twisting dual pulses with a high degree of freedom.

A polarization-twisting dual-pulse (PTDP) system is demonstrated using a modified Michelson interferometer (MI), in which a pellicle beam splitter is inserted into each arm. By tuning the positions of the end mirrors and pellicle beam splitters in the MI, the polarization-twisting frequency, the helicity, and the interval between two pulses can be individually manipulated. This PTDP generation system has a high degree of freedom in terms of tuning and has applications in the study of helicity dynamics in quantum matter, particularly in the terahertz (THz) regime.

π-Extended Coumarins Derived with Nonhydrolyzable Iminophosphoranes as Two-Photon-Excited Fluorophores.

Novel coumarin-iminophosphorane (IPP) fluorophores that have stable resonance contributions from aza-ylides were formed by using the nonhydrolysis Staudinger reaction. The N═P formation reaction kinetics obey the conventional Staudinger reaction. The absorption and emission profiles of the coumarin-IPP derivatives can be fine-tuned: an electron-donating group at PPh3 enhances absorption and fluorescence, whereas an electron-withdrawing group at C-3 drives absorption and emission peaks toward blue-light wavelengths. Two-photon adsorption, accompanied by anti-Stokes fluorescence, is achieved under near-infrared femtosecond laser excitation.

Ultrafast Giant Photostriction of Epitaxial Strontium Iridate Film with Superior Endurance.

Photostriction, optical stimulus driven mechanical deformation in materials, provides a solution toward next-generation technology. Here, the giant photostriction (∼2% change of lattice) of epitaxial strontium iridate (SrIrO3) films under illumination at room temperature is revealed via power-dependent Raman scattering, which is significantly larger as compared to conventional inorganic materials. The time scale and mechanism of this giant photostriction in SrIrO3 are further studied through time-resolved transient reflectivity measurements. The main mechanism is determined to be the electron-phonon coupling. In addition, we find that such an exotic behavior happens within few picoseconds and remains up to 107 cyclic on/off operations. The observation of giant photostriction in SrIrO3 films with superior endurance promises the advance of shape responsive solids that are sensitive to environmental stimuli, which could be widely utilized for multifunctional optoelectronics and optomechanical devices.

Intrinsic Carrier Transport of Phase-Pure Homologous 2D Organolead Halide Hybrid Perovskite Single Crystals.

This work reveals the intrinsic carrier transport behavior of 2D organolead halide perovskites based on phase-pure homologous (n = 1, 2, and 3) Ruddelsden-Popper perovskite (RPP) (BA)2 (MA)n -1 Pbn I3n+1 single crystals. The 2D perovskite field effect transistors with high-quality exfoliated 2D perovskite bulk crystals are fabricated, and characteristic output and transfer curves are measured from individual single-crystal flakes with various n values under different temperatures. Unipolar n-type transport dominated the electrical properties of all these 2D RPP single crystals. The transport behavior of the 2D organolead halide hybrid perovskites exhibits a strong dependence on the n value and the mobility substantially increases as the ratio of the number of inorganic perovskite slabs per organic spacer increases. By extracting the effect of contact resistances, the corrected mobility values for n = 1, 2, and 3 are 2 × 10-3 , 8.3 × 10-2 , and 1.25 cm2 V-1 s-1 at 77 K, respectively. Furthermore, by combining temperature-dependent electrical transport and optical measurements, it is found that the origin of the carrier mobility dependence on the phase transition for 2D organolead halide perovskites is very different from that of their 3D counterparts. Our findings offer insight into fundamental carrier transport behavior of 2D organic-inorganic hybrid perovskites based on phase-pure homologous single crystals.

Robust terahertz polarizers with high transmittance at selected frequencies through Si wafer bonding technologies.

Terahertz (THz) polarizers with robust structure and high transmittance are demonstrated using 3D-integrated circuit (IC) technologies. A Cu wire-grid polarizer is sealed and well protected by Si-bonded wafers through a low-temperature eutectic bonding method. Deep reactive-ion etching is used to fabricate the anti-reflection (AR) layers on outward surfaces of bonded wafers. The extinction ratio and transmittance of polarizers are between 20 dB and 33 dB, and 13 dB and 27 dB for 10 µm and 20 µm pitch wire-grids, respectively, and 100% at central frequency, depending on frequency and AR layer thickness. The process of polarizer fabrication is simple from mature semiconductor manufacturing techniques that lead to high yield, low cost, and potential for THz applications.

THz emission from organic cocrystalline salt: 2, 6-diaminopyridinium-4-nitrophenolate-4-nitrophenol.

We report few-cycle THz pulses emission from a novel organic crystal 2,6-diaminopyridinium-4-nitrophenolate-4-nitrophenol (DAP+NP-NP). The observed amplitude of the THz electric field from a DAP+NP-NP crystal is comparable with that from a ZnTe single crystal under the same optical pumping conditions. Both the waveform and spectra of the THz radiation from DAP+NP-NP are similar to those from ZnTe. We conclude that a high quality DAP+NP-NP crystal would be a high potential candidate in THz generation and applications.

Controlling the carrier-envelope phase of single-cycle mid-infrared pulses with two-color filamentation.

Carrier-envelope phase (CEP) of single-cycle pulses generated through two-color filamentation has been investigated. We have observed a particular behavior of the phase: the phase of high-frequency components of the generated pulses changes continuously and linearly with the relative phase between the two-color input pulses, whereas the phase of the low-frequency components takes only two discrete values. The transition of the phase behavior has been clearly observed by using frequency-resolved optical gating capable of CEP determination. We have found out that such a phase behavior is a unique feature of single-cycle pulses generated with a passive CEP stabilization scheme.

Dual-plasmonic Au@Cu7S4 yolk@shell nanocrystals for photocatalytic hydrogen production across visible to near infrared spectral region.

Near infrared energy remains untapped toward the maneuvering of entire solar spectrum harvesting for fulfilling the nuts and bolts of solar hydrogen production. We report the use of Au@Cu7S4 yolk@shell nanocrystals as dual-plasmonic photocatalysts to achieve remarkable hydrogen production under visible and near infrared illumination. Ultrafast spectroscopic data reveal the prevalence of long-lived charge separation states for Au@Cu7S4 under both visible and near infrared excitation. Combined with the advantageous features of yolk@shell nanostructures, Au@Cu7S4 achieves a peak quantum yield of 9.4% at 500 nm and a record-breaking quantum yield of 7.3% at 2200 nm for hydrogen production in the absence of additional co-catalysts. The design of a sustainable visible- and near infrared-responsive photocatalytic system is expected to inspire further widespread applications in solar fuel generation. In this work, the feasibility of exploiting the localized surface plasmon resonance property of self-doped, nonstoichiometric semiconductor nanocrystals for the realization of wide-spectrum-driven photocatalysis is highlighted.

Three-dimensional ultrafast charge-density-wave dynamics in CuTe.

Charge density waves (CDWs) involved with electronic and phononic subsystems simultaneously are a common quantum state in solid-state physics, especially in low-dimensional materials. However, CDW phase dynamics in various dimensions are yet to be studied, and their phase transition mechanism is currently moot. Here we show that using the distinct temperature evolution of orientation-dependent ultrafast electron and phonon dynamics, different dimensional CDW phases are verified in CuTe. When the temperature decreases, the shrinking of c-axis length accompanied with the appearance of interchain and interlayer interactions causes the quantum fluctuations (QF) of the CDW phase until 220 K. At T < 220 K, the CDWs on the different ab-planes are finally locked with each other in anti-phase to form a CDW phase along the c-axis. This study shows the dimension evolution of CDW phases in one CDW system and their stabilized mechanisms in different temperature regimes.

High-speed scanless entire bandwidth mid-infrared chemical imaging.

Mid-infrared spectroscopy probes molecular vibrations to identify chemical species and functional groups. Therefore, mid-infrared hyperspectral imaging is one of the most powerful and promising candidates for chemical imaging using optical methods. Yet high-speed and entire bandwidth mid-infrared hyperspectral imaging has not been realized. Here we report a mid-infrared hyperspectral chemical imaging technique that uses chirped pulse upconversion of sub-cycle pulses at the image plane. This technique offers a lateral resolution of 15 µm, and the field of view is adjustable between 800 µm × 600 µm to 12 mm × 9 mm. The hyperspectral imaging produces a 640 × 480 pixel image in 8 s, which covers a spectral range of 640-3015 cm-1, comprising 1069 wavelength points and offering a wavenumber resolution of 2.6-3.7 cm-1. For discrete frequency mid-infrared imaging, the measurement speed reaches a frame rate of 5 kHz, the repetition rate of the laser. As a demonstration, we effectively identified and mapped different components in a microfluidic device, plant cell, and mouse embryo section. The great capacity and latent force of this technique in chemical imaging promise to be applied to many fields such as chemical analysis, biology, and medicine.

Enhance high harmonic generation (HHG) efficiency via compact multi-plate continuum post-compression for time-resolved angle-resolved photoemission spectroscopy.

Time-resolved angle-resolved photoemission spectroscopy (Tr-APRES) gives direct insight into electron dynamics by providing temporal-, energy-, and momentum-resolved information in one experiment. A major obstacle to using high harmonic generation (HHG) probe pulses for photoemission spectroscopy is the low conversion efficiency, that is, the low flux of probe photons. We use a Yb-KGW based duo-laser source with an oscillator to pump two separate amplifiers and generate two synchronized pulsed laser sources with average energies of 7.5 and 6 W. By using the multiplate continuum method and chirped mirrors, the resulting flux of HHG photons at 33-70 eV can be increased 50-fold (up to 1011 photons/s) by using post-compressed 30 fs pulses compared with the photon flux generated by the fundamental 190 fs pulses. Moreover, pulses from the 6 W amplifier are used to pump an optical parametric amplifier that can vary the wavelengths for photoexcitation. The system performance is demonstrated by applying Tr-ARPES to single-crystal graphite. The front tilt broadening is significantly suppressed by the off-plane mounted conical grating, leading to a 184 fs temporal resolution that is mainly limited by the pump pulse. The energy resolution is 176 meV.

Optimal Te-doping in GaSe for non-linear applications.

Centimeter-sized Te-doped GaSe ingots were grown from the charge compositions of GaSe with nominals 0.05, 0.1, 0.5, 1, and 3 mass% Te, which were identified as ε-GaSe:Te (0.01, 0.07, 0.38, 0.67, and 2.07 mass%) single crystals. The evolution of the absorption peaks of the phonon modes E'(2) (≈ 0.584 THz) and E"(2) (1.77 THz) on Te-doping in GaSe:Te crystals was studied by THz time-domain spectroscopy. This study proposes that the evolution of both E'(2) and E''(2) absorption peaks correlates well with the optical quality of Te-doped GaSe crystals, which was confirmed by experimental results on the efficiency of THz generation by optical rectification. Maximal intensity of the absorption peak of the rigid layer mode E'(2) is proposed as a criterion for identification of optimal Te-doping in GaSe crystals.

Widely linear and non-phase-matched optical-to-terahertz conversion on GaSe:Te crystals.

We demonstrate the widely linear and broadband terahertz (THz) generation on GaSe:Te crystals by femtosecond laser pulses. It was found that the dopant, Te atoms, in GaSe crystals significantly enhances the efficiency of THz generation, and its central frequency can be tuned by varying the crystal thickness through non-phase-matched optical rectification. Moreover, the wide-ranging linearity for the optical-to-THz conversion and central-frequency-tunable THz generation promise for GaSe:Te crystals to be potential materials for high-power (>1.36 µW) THz applications.