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. Stereolithography and femtosecond laser direct writing respectively achieved their resolutions of ~50 µm and ~100 nm. However, fabricating glass structures with centimeter dimensions and sub-micron features remains challenging. Presented here, our study effectively bridges the gap through engineering suitable materials and utilizing one-photon micro-stereolithography (OµSL)-based 3D printing, which flexibly creates transparent and high-performance fused silica glass components with complex, 3D sub-micron architectures. Comprehensive characterizations confirm that the final material is stoichiometrically pure silica with high quality, defect-free morphology, and excellent optical properties. Homogeneous volumetric shrinkage further facilitates the smallest voxel, reducing the size from 2.0 × 2.0 × 1.0 µm3 to 0.8 × 0.8 × 0.5 µm3. This approach can be used to produce fused silica glass components with various 3D geometries featuring sub-micron details and millimetric dimensions. This showcases promising prospects in diverse fields, including micro-optics, microfluidics, mechanical metamaterials, and engineered surfaces.

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. Herein, using a single crystals platform of quasi-2D (BA)2 (MA)n-1 Pbn I3n+1 (n > 1) perovskites, the femtosecond laser ablation approach to design and write the LESs with a high spatial resolution is reported. Fundamentally, these LESs are of smaller bandgap 3D MAPbI3 nanocrystals which are formed by the laser-induced BA escaping from the lattice and thus the lattice shrinkage from quasi-2D to 3D structures. Furthermore, by covering the crystal with tape, an additional high-energy emission state corresponding to the reformation of (BA)2 PbI4 (n = 1) within the irradiation region is generated. This work presents a simple and efficient protocol to manually write LESs on single crystals and thus lays the foundation for utilizing these LESs to further enhance the performance of future photoelectronic devices.

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 SiO2 can be either amorphous glass or polycrystalline cristobalite controlled by the sintering process. The 3D-printed nanostructures demonstrate attractive optical properties. For instance, the fabricated micro-toroid optical resonators can reach quality factors (Q) of over 104. Moreover, and importantly for optical applications, doping and codoping of rare-earth salts such as Er3+, Tm3+, Yb3+, Eu3+ and Nd3+ can be directly implemented in the printed SiO2 structures, showing strong photoluminescence at the desired wavelengths. This technique shows the potential for building integrated microphotonics with silica via 3D printing.

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. As a consequence, the quasiparticle bandgaps of ML MoSe2, ML MoS2, BL MoSe2, and BL WSe2 are determined to be 2.07, 2.11, 1.67, and 1.81 eV, respectively. Our work reveals a general picture for the hot carrier relaxation dynamics in atomically thin TMDs and offers an effective experimental approach in probing the bandgaps of TMDs under ambient conditions.

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. The synthesized all-inorganic lead-free perovskite derivative, Cs3 Bi2 I9 , exhibits strong light-matter interaction and parity-dependent optically addressable valley degree of freedom. Robust optical helicity in all odd-layer-number crystals with inversion symmetry breaking is observed, indicating excitonic coherence extending well beyond 11 layers. The excellent optical and valley properties of Cs3 Bi2 I9 arise from the unique parallel bands, according to first principles calculations. This discovery points to new materials design principles for scalable valleytronic devices and demonstrates the promise of perovskite derivatives beyond energy applications.

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

The original version of this Article omitted an affiliation of Xiewen Wen: 'College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, China'. This has been corrected in both the PDF and HTML versions of the Article.

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. Our observations reveal unexpected ultrafast formation of tightly bound interlayer excitons between conducting graphene and semiconducting MoSe2. The result suggests carriers in the doped graphene are no longer massless, and an effective mass as small as one percent of free electron mass is sufficient to confine carriers within a 2D hetero space with energy 10 times larger than the room-temperature thermal energy. The interlayer excitons arise within 1 ps. Their formation effectively blocks charge recombination and improves charge separation efficiency for more than one order of magnitude.

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, MoS2, WS2, h-BN, TiS2, NbS2, Bi2Se3, MoTe2, Sb2Te3, etc., using a cryo-mediated liquid-phase exfoliation and fracturing process. The method relies on liquid nitrogen pretreatment of bulk layered materials before exfoliation and breakdown into atomically thin two-dimensional quantum dots of few-nanometer lateral dimensions, exhibiting size-confined optical properties. This process is efficient for a variety of common solvents with a wide range of surface tension parameters and eliminates the use of surfactants, resulting in pristine quantum dots without surfactant covering or chemical modification.

Three-dimensional mesostructures as high-temperature growth templates, electronic cellular scaffolds, and self-propelled microrobots.

Recent work demonstrates that processes of stress release in prestrained elastomeric substrates can guide the assembly of sophisticated 3D micro/nanostructures in advanced materials. Reported application examples include soft electronic components, tunable electromagnetic and optical devices, vibrational metrology platforms, and other unusual technologies, each enabled by uniquely engineered 3D architectures. A significant disadvantage of these systems is that the elastomeric substrates, while essential to the assembly process, can impose significant engineering constraints in terms of operating temperatures and levels of dimensional stability; they also prevent the realization of 3D structures in freestanding forms. Here, we introduce concepts in interfacial photopolymerization, nonlinear mechanics, and physical transfer that bypass these limitations. The results enable 3D mesostructures in fully or partially freestanding forms, with additional capabilities in integration onto nearly any class of substrate, from planar, hard inorganic materials to textured, soft biological tissues, all via mechanisms quantitatively described by theoretical modeling. Illustrations of these ideas include their use in 3D structures as frameworks for templated growth of organized lamellae from AgCl-KCl eutectics and of atomic layers of WSe2 from vapor-phase precursors, as open-architecture electronic scaffolds for formation of dorsal root ganglion (DRG) neural networks, and as catalyst supports for propulsive systems in 3D microswimmers with geometrically controlled dynamics. Taken together, these methodologies establish a set of enabling options in 3D micro/nanomanufacturing that lie outside of the scope of existing alternatives.

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. Our study provides not only insight understanding but also new approaches towards the broadband graphene absorber.

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. The observations therefore explain how the remarkable charge transfer rate and photocurrent generation are achieved even with the aforementioned momentum mismatch and excitonic localization in 2D heterostructures and devices.

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. It is found that the photo-generation of excited carriers occurs within two hundred fs and the relaxation of the carriers is tens of ps. The electron-phonon coupling between the excitations of electrons and the phonon mode E1u of MoS2 is also directly observed. The electron excitation shifts the frequency of the phonon mode 9 cm(-1) higher, resulting in an absorption peak at 391 cm(-1) and a bleaching peak at 382 cm(-1). The frequency shift diminishes with the relaxation of the carriers.

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. More and larger clusters form in solutions that are relatively more concentrated and which include a larger cation. In KSCN solutions, the shortest anionic distance in the ion clusters is the same as that in the KSCN crystal. The rotational time of the anion and the nonresonant vibrational energy transfer time with a gap of 75 cm(-1) in the KSCN saturated solution are very similar to those in the KSCN crystal. However, the KSCN ion clusters are closer in structure to the melt. The clusters form an interconnected network with random ionic orientations. Because of ion clustering, the anion and water dynamics behave distinctly in the same solutions. At high concentrations, the anion rotation significantly slows down because of the increase in the size of the ion clusters, but the slowdown amplitude of water rotation is very modest because many of the water molecules still remain in the "bulk" state due to ion clustering. The rotational dynamics of both water and anions are slower in a solution with a smaller cation, primarily because a smaller cation has a stronger cation/anion interaction and a cation/water interaction that leads to more water molecules confined in the ion clusters. Adding ions or molecules into the KSCN solutions can perturb the ion clusters. Weakly hydrated anions can participate in clustering and form mixed ion clusters with KSCN, and strongly hydrated anions can reduce the effective water molecules solvating KSCN and facilitate the formation of more and larger KSCN ion clusters. Similarly, molecules which can strongly bind to SCN(-) prefer to participate in the KSCN ion clusters. Molecules which are strongly hydrated prefer to remain hydrated and facilitate the ion clustering of KSCN.

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. Instead, the experimental energy-gap dependences can be quantitatively reproduced by the dephasing mechanism. A simple theoretical derivation shows that the fast molecular motions in liquids randomize the modulations on the energy donor and acceptor by phonons and diminish the phonon compensation efficiency on energy transfer. Estimations based on the theoretical derivations suggest that, for most nonresonant intermolecular vibrational-energy transfers in liquids with energy gaps smaller than the thermal energy, the dephasing mechanism dominates the energy-transfer process.

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). The device is characterized both theoretically and experimentally. Analyses show that the multiple-plasmon-resonance is the key for the broadband feature and the phase-shift difference of the two reflection components is critical for the polarization conversion. The approach demonstrated in the work can be useful for constructing building blocks for THz polarimetry.

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. inverted energy-gap dependent energy transfer rates and opposite temperature dependences of resonant and nonresonant energy transfer rates. Two competing mechanisms are proposed to be responsible for the experimental observations. The first one is the dephasing mechanism in which the measured energy transfer rate originates from the dephasing of the energy donor-acceptor coherence, and the second one is the phonon-compensation mechanism derived from the second order perturbation. It is found that both the nonresonant energy transfers in the liquids and resonant energy transfers in both liquids and solids can be well described by the first mechanism. The second mechanism explains the nonresonant energy transfers in one series of the solid samples very well.

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. In the crystalline samples, the closest anion distance was determined to be 3.9 ± 0.3 Å, consistent with the XRD result. In the 1.8 and 1 M KSCN aqueous solutions, the anion distances in the ion clusters were determined to be 4.4 ± 0.4 Å. The clustered anion distances in aqueous solutions are very similar to the closest anion distance in the KSCN crystal but significantly shorter than the average anion distance (0.94-1.17 nm) in the aqueous solutions if ion clustering did not occur. The result suggests that ions in the strong electrolyte aqueous solutions can form clusters inside of which they have direct contact with each other.

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. The results demonstrate that the vibrational cross angle method based on the multiple-mode approach can potentially become a structural tool for determining molecular conformations. The major challenges for the method to become a general molecular structural tool are discussed, and some approaches to address them are proposed.

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. The reorientational time constants follow the order of Li(+) > Na(+) > K(+) ~/= Cs(+). The changes of rotational time constants of SCN(-) at various concentrations scale almost linearly with the changes of solution viscosity, but those of water molecules do not. In addition, the concentration-dependent amplitudes of dynamical changes are much more significant in the Li(+) and Na(+) solutions than those in the K(+) and Cs(+) solutions. Further investigations on the systems with the ultrafast vibrational energy exchange method and molecular dynamics simulations provide an explanation for the observations: the observed rotational dynamics are the balanced results of ion clustering and cation/anion/water direct interactions. In all the solutions at high concentrations (>5 M), substantial amounts of ions form clusters. The structural inhomogeneity in the solutions leads to distinct rotational dynamics of water and anions. The strong interactions of Li(+) and Na(+) because of their relatively large charge densities with water molecules and SCN(-) anions, in addition to the likely geometric confinements because of ion clustering, substantially slow down the rotations of SCN(-) anions and water molecules inside the ion clusters. The interactions of K(+) and Cs(+) with water or SCN(-) are much weaker. The rotations of water molecules inside ion clusters of K(+) and Cs(+) solutions are not significantly different from those of other water species so that the experimentally observed rotational relaxation dynamics are only slightly affected by the ion concentrations.

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. We also demonstrated that the correlation between the anisotropy value of heat signal and the relative molecular orientations can be quantitatively calculated.