One-photon three-dimensional printed fused silica glass with sub-micron features.

The applications of silica-based glass have evolved alongside human civilization for thousands of years. High-precision manufacturing of three-dimensional (3D) fused silica glass objects is required in various industries, ranging from everyday life to cutting-edge fields. Advanced 3D printing technologies have emerged as a potent tool for fabricating arbitrary glass objects with ultimate freedom and precision.

Designable Layer Edge States in Quasi-2D Perovskites Induced by Femtosecond Pulse Laser.

The low-energy layer edge states (LESs) from quasi 2D hybrid perovskite single crystals have shown great potential because of their nontrivial photoelectrical properties. However, the underlying formation mechanism of the LESs still remains controversial. Also, the presence or creation of the LESs is of high randomness due to the lack of proper techniques to manually generate these LESs.

3D-printed silica with nanoscale resolution.

Fabricating inorganic materials with designed three-dimensional nanostructures is an exciting yet challenging area of research and industrial application. Here, we develop an approach to 3D print high-quality nanostructures of silica with sub-200 nm resolution and with the flexible capability of rare-earth element doping. The printed SiO can be either amorphous glass or polycrystalline cristobalite controlled by the sintering process.

Determining Quasiparticle Bandgap of Two-Dimensional Transition Metal Dichalcogenides by Observation of Hot Carrier Relaxation Dynamics.

Using excitation-energy-scanning ultrafast infrared microspectroscopy, the excess energy-dependent hot carrier relaxation dynamics in atomically thin two-dimensional transition metal dichalcogenides (2D TMDs) after femtosecond photoexcitation was directly monitored. A good linear relationship between the carrier relaxation time and the excitation wavelength is observed for all measured monolayer (ML) and bilayer (BL) TMD samples, which allows us to determine their quasiparticle bandgaps as well as corresponding exciton binding energies. A carrier-optical-phonon scattering-mediated cascading-relaxation model is proposed, which can perfectly describe all the measured dynamics.

Perovskite-Derivative Valleytronics.

Halide perovskites are revolutionizing the renewable energy sector owing to their high photovoltaic efficiency, low manufacturing cost, and flexibility. Their remarkable mobility and long carrier lifetime are also valuable for information technology, but fundamental challenges like poor stability under an electric field prevent realistic applications of halide perovskites in electronics. Here, it is discovered that valleytronics is a promising route to leverage the advantages of halide perovskites and derivatives for information storage and processing.

Ultrafast probes of electron-hole transitions between two atomic layers.

Phase transitions of electron-hole pairs on semiconductor/conductor interfaces determine fundamental properties of optoelectronics. To investigate interfacial dynamical transitions of charged quasiparticles, however, remains a grand challenge. By employing ultrafast mid-infrared microspectroscopic probes to detect excitonic internal quantum transitions and two-dimensional atomic device fabrications, we are able to directly monitor the interplay between free carriers and insulating interlayer excitons between two atomic layers.

Cryo-mediated exfoliation and fracturing of layered materials into 2D quantum dots.

Atomically thin quantum dots from layered materials promise new science and applications, but their scalable synthesis and separation have been challenging. We demonstrate a universal approach for the preparation of quantum dots from a series of materials, such as graphite, MoS, WS, h-BN, TiS, NbS, BiSe, MoTe, SbTe, etc., using a cryo-mediated liquid-phase exfoliation and fracturing process.

Broadband light absorption in graphene ribbons by canceling strong coupling at subwavelength scale.

We theoretically investigate the broadband light absorption in the THz range by canceling the strong coupling in an array of graphene ribbons at subwavelength scale. A series of resonators with different absorption frequencies can achieve a broadband absorber, however, the suppression of absorption always accompanies since the mutual coupling between resonators cause the mode splitting. By adjusting the near- and far-field coupling between the plasmon resonances of the graphene ribbon array to the critical point, the absorption linewidth is broadened for almost one magnitude larger than that of individual graphene ribbon, to be ~1 THz.

Ultrafast formation of interlayer hot excitons in atomically thin MoS2/WS2 heterostructures.

Van der Waals heterostructures composed of two-dimensional transition-metal dichalcogenides layers have recently emerged as a new family of materials, with great potential for atomically thin opto-electronic and photovoltaic applications. It is puzzling, however, that the photocurrent is yielded so efficiently in these structures, despite the apparent momentum mismatch between the intralayer/interlayer excitons during the charge transfer, as well as the tightly bound nature of the excitons in 2D geometry. Using the energy-state-resolved ultrafast visible/infrared microspectroscopy, we herein obtain unambiguous experimental evidence of the charge transfer intermediate state with excess energy, during the transition from an intralayer exciton to an interlayer exciton at the interface of a WS2/MoS2 heterostructure, and free carriers moving across the interface much faster than recombining into the intralayer excitons.

Electron-phonon interactions in MoS2 probed with ultrafast two-dimensional visible/far-infrared spectroscopy.

An ultrafast two-dimensional visible/far-IR spectroscopy based on the IR/THz air biased coherent detection method and scanning the excitation frequencies is developed. The method allows the responses in the far-IR region caused by various electronic excitations in molecular or material systems to be observed in real time. Using the technique, the relaxation dynamics of the photo-excited carriers and electron/phonon coupling in bulk MoS2 are investigated.

Vibrational energy transfer: an angstrom molecular ruler in studies of ion pairing and clustering in aqueous solutions.

The methodology and principle using vibrational energy transfer to measure molecular distances in liquids are introduced. The application of the method to the studies of ion pairing and clustering in strong electrolyte aqueous solutions is demonstrated with MSCN aqueous solutions where M = Li, Na, K, Cs, and NH4. Experiments suggest that ions in the concentrated aqueous solutions can form substantial quantities of ion clusters in which both cations and anions are involved.

Nonresonant energy transfers independent on the phonon densities in polyatomic liquids.

Energy-gap-dependent vibrational-energy transfers among the nitrile stretches of KSCN/KS(13)CN/KS(13)C(15)N in D2O, DMF, and formamide liquid solutions at room temperature were measured by the vibrational-energy-exchange method. The energy transfers are slower with a larger energy donor/acceptor gap, independent of the calculated instantaneous normal mode ("phonons" in liquids) densities or the terahertz absorption spectra. The energy-gap dependences of the nonresonant energy transfers cannot be described by phonon compensation mechanisms with the assumption that phonons are the instantaneous normal modes of the liquids.

Broadband THz reflective polarization rotator by multiple plasmon resonances.

We demonstrate a metamaterials-based THz broadband polarization rotator which is able to rotate linearly polarized THz wave by 90 degree within a wide frequency range (0.44 to 0.76 THz).

Intermolecular vibrational energy transfers in liquids and solids.

Resonant and nonresonant intermolecular vibrational energy transfers in KSCN/KSC(13)N/KS(13)C(15)N aqueous and DMF solutions and crystals are studied. Both energy-gap and temperature dependent measurements reveal some surprising results, e.g.

Molecular distances determined with resonant vibrational energy transfers.

In general, intermolecular distances in condensed phases at the angstrom scale are difficult to measure. We were able to do so by using the vibrational energy transfer method, an ultrafast vibrational analogue of Förster resonance energy transfer. The distances among SCN(-) anions in KSCN crystals and ion clusters of KSCN aqueous solutions were determined with the method.

Molecular conformations of crystalline L-cysteine determined with vibrational cross angle measurements.

The molecular conformations of crystalline L-cysteine prepared in its orthorhombic form were determined by the vibrational cross angle measurements. Its major dihedral angles of chemical bonds determined by this method are consistent with the results from diffraction experiments. In addition, the relative orientations of the chemical bonds associated with the hydrogen atoms of the NH3(+) group and the thiol group are also determined.

Cation effects on rotational dynamics of anions and water molecules in alkali (Li+, Na+, K+, Cs+) thiocyanate (SCN-) aqueous solutions.

Waiting time dependent rotational anisotropies of SCN(-) anions and water molecules in alkali thiocyanate (XSCN, X = Li, Na, K, Cs) aqueous solutions at various concentrations were measured with ultrafast infrared spectroscopy. It was found that cations can significantly affect the reorientational motions of both water molecules and SCN(-) anions. The dynamics are slower in a solution with a smaller cation.

Relative intermolecular orientation probed via molecular heat transport.

In this work, through investigating a series of liquid, glassy, and crystalline samples with ultrafast multiple-mode 2D IR and IR transient absorption methods, we demonstrated that the signal anisotropy of vibrational relaxation-induced heat effects is determined by both relative molecular orientations and molecular rotations. If the relative molecular orientations are randomized or molecular rotations are fast compared to heat transfer, the signal anisotropy of heat effects is zero. If the relative molecular orientations are anisotropic and the molecular rotations are slow, the signal anisotropy of heat effects can be nonzero, which is determined by the relative orientations of the energy source mode and the heat sensor mode within the same molecule and in different molecules.

Probing ion/molecule interactions in aqueous solutions with vibrational energy transfer.

Interactions between model molecules representing building blocks of proteins and the thiocyanate anion, a strong protein denaturant agent, were investigated in aqueous solutions with intermolecular vibrational energy exchange methods. It was found that thiocyanate anions are able to bind to the charged ammonium groups of amino acids in aqueous solutions. The interactions between thiocyanate anions and the amide groups were also observed.

Ion association in aqueous solutions probed through vibrational energy transfers among cation, anion, and water molecules.

KSCN and NH4SCN aqueous solutions were investigated with intermolecular vibrational energy transfer methods. In a KSCN/H2O (1/10 molar ratio) solution, 90% of the initial excitation of the CN stretch (~2066 cm(-1)) of the SCN(-) anion is transferred to the HOH bending mode (~1636 cm(-1)) of water molecules with an energy transfer time constant 3.1 ps.

Nonresonant and resonant mode-specific intermolecular vibrational energy transfers in electrolyte aqueous solutions.

The donor/acceptor energy mismatch and vibrational coupling strength dependences of interionic vibrational energy transfer kinetics in electrolyte aqueous solutions were investigated with ultrafast multiple-dimensional vibrational spectroscopy. An analytical equation derived from the Fermi's Golden rule that correlates molecular structural parameters and vibrational energy transfer kinetics was found to be able to describe the intermolecular mode specific vibrational energy transfer. Under the assumption of the dipole-dipole approximation, the distance between anions in the aqueous solutions was obtained from the vibrational energy transfer measurements, confirmed with measurements on the corresponding crystalline samples.

Mapping molecular conformations with multiple-mode two-dimensional infrared spectroscopy.

The multiple-mode two-dimensional infrared (2D-IR) spectrum in a broad frequency range from 1000 to 3200 cm(-1) of a 1-cyanovinyl acetate solution in CCl(4) is reported. By analyzing its relative orientations of the transition dipole moments of normal modes that cover vibrations of all chemical bonds, the three-dimensional molecular conformations and their population distributions of 1-cyanovinyl acetate are obtained, with the aid of quantum chemistry calculations that translate the experimental transition dipole moment cross angles into the cross angles among chemical bonds.

Mode-specific intermolecular vibrational energy transfer. II. Deuterated water and potassium selenocyanate mixture.

Vibrational energy transfer from the first excited state (2635 cm(-1)) of the O-D stretch of deuterated water (D(2)O) to the 0-1 transition (2075 cm(-1)) of the CN stretch of potassium selenocyanate (KSeCN) in their 2.5:1 liquid mixture was observed with a multiple-mode two dimensional infrared spectroscopic technique. Despite the big energy mismatch (560 cm(-1)) between the two modes, the transfer is still very efficient with a time constant of 20 ps.