All-Optical Reconfigurable Excitonic Charge States in Monolayer MoS2.

Excitons are quasi-particles composed of electron-hole pairs through Coulomb interaction. Due to the atomic-thin thickness, they are tightly bound in monolayer transition metal dichalcogenides (TMDs) and dominate their optical properties. The capability to manipulate the excitonic behavior can significantly influence the photon emission or carrier transport performance of TMD-based devices. However, on-demand and region-selective manipulation of the excitonic states in a reversible manner remains challenging so far. Herein, harnessing the coordinated effect of femtosecond-laser-driven atomic defect generation, interfacial electron transfer, and surface molecular desorption/adsorption, we develop an all-optical approach to manipulate the charge states of excitons in monolayer molybdenum disulfide (MoS2). Through steering the laser beam, we demonstrate reconfigurable optical encoding of the excitonic charge states (between neutral and negative states) on a single MoS2 flake. Our technique can be extended to other TMDs materials, which will guide the design of all-optical and reconfigurable TMD-based optoelectronic and nanophotonic devices.

Polarization-dependent Bloch oscillations in optical waveguides.

Optical systems provide a new and practical platform for studying Bloch oscillations. This study investigates the fundamental-mode propagation of polarization-dependent Bloch oscillations. By using the three-dimensional properties of femtosecond laser direct writing, we fabricate a polymer-based gradient waveguide array and determine the Bloch oscillations under different polarization inputs by using the birefringence gradient and the equivalent refractive index, thus exhibiting a polarization-dependent Bloch period. Our results provide a new, to the best of our knowledge, paradigm for two-dimensional optical Bloch modes and highlight the influence of optical polarization in the same system, which provides a possibility to observe richer physics related to Bloch oscillations in one structure.

Light-Driven Magnetic Encoding for Hybrid Magnetic Micromachines.

Remote manipulation of a micromachine under an external magnetic field is significant in a variety of applications. However, magnetic manipulation requires that either the target objects or the fluids should be ferromagnetic or superparamagnetic. To extend the applicability, we propose a versatile optical printing technique termed femtosecond laser-directed bubble microprinting (FsLDBM) for on-demand magnetic encoding. Harnessing Marangoni convection, evaporation flow, and capillary force for long-distance delivery, near-field attraction, and printing, respectively, FsLDBM is capable of printing nanomaterials on the solid-state substrate made of arbitrary materials. As a proof-of-concept, we actuate a 3D polymer microturbine under a rotating magnetic field by implementing γ-Fe2O3 nanomagnets on its blade. Moreover, we demonstrate the magnetic encoding on a living daphnia and versatile manipulation of the hybrid daphnia. With its general applicability, the FsLDBM approach provides opportunities for magnetic control of general microstructures in a variety of applications, such as smart microbots and biological microsurgery.

Optothermal Manipulations of Colloidal Particles and Living Cells.

Optical manipulation techniques are important in many fields. For instance, they enable bottom-up assembly of nanomaterials and high-resolution and in situ analysis of biological cells and molecules, providing opportunities for discovery of new materials, medical diagnostics, and nanomedicines. Traditional optical tweezers have their applications limited due to the use of rigorous optics and high optical power. New strategies have been established for low-power optical manipulation techniques. Optothermal manipulation, which exploits photon-phonon conversion and matter migration under a light-controlled temperature gradient, is one such emerging technique. Elucidation of the underlying physics of optothermo-matter interaction and rational engineering of optical environments are required to realize diverse optothermal manipulation functionalities. This Account covers the working principles, design concepts, and applications of a series of newly developed optothermal manipulation techniques, including bubble-pen lithography, opto-thermophoretic tweezers, opto-thermoelectric tweezers, optothermal assembly, and opto-thermoelectric printing. In bubble-pen lithography, optical heating of a plasmonic substrate generates microbubbles at the solid-liquid interface to print diverse colloidal particles on the substrates. Programmable bubble printing of semiconductor quantum dots on different substrates and haptic control of printing have also been achieved. The key to optothermal tweezers is the ability to deliver colloidal particles from cold to hot regions of a temperature gradient or a negative Soret effect. We explore different driving forces for the two types of optothermal tweezers. Opto-thermophoretic tweezers rely on an abnormal permittivity gradient built by structured solvent molecules in the electric double layer of colloidal particles and living cells in response to heat-induced entropy, and opto-thermoelectric tweezers exploit a thermophoresis-induced thermoelectric field for the low-power manipulation of small nanoparticles with minimum diameter around 20 nm. Furthermore, by incorporating depletion attraction into the optothermal tweezers system as particle-particle or particle-substrate binding force, we have achieved bottom-up assembly and reconfigurable optical printing of artificial colloidal matter. Beyond optothermal manipulation techniques in liquid environments, we also review recent progress of gas-phase optothermal manipulation based on photophoresis. Photophoretic trapping and transport of light-absorbing materials have been achieved through optical engineering to tune particle-molecule interactions during optical heating, and a novel optical trap display has been demonstrated. An improved understanding of the colloidal response to temperature gradients will surely facilitate further innovations in optothermal manipulation. With their low-power operation, simple optics, and diverse functionalities, optothermal manipulation techniques will find a wide range of applications in life sciences, colloidal science, materials science, and nanoscience, as well as in the developments of colloidal functional devices and nanomedicine.

Digital manufacturing of advanced materials: challenges and perspective.

The rapid development in materials science and engineering requests the manufacturing of materials in a more rational and designable manner. Beyond traditional manufacturing techniques, such as casting and coating, digital control of material morphology, composition, and structure represents a highly integrated and versatile approach. Digital manufacturing systems enable users to fabricate freeform materials, which lead to new functionalities and applications. Digital additive manufacturing (AM), which is a layer-by-layer fabrication approach to create three-dimensional (3D) products with complex geometries, is changing the way materials manufacturing is approached in traditional industry. More recently, digital printing of chemically synthesized colloidal nanoparticles has paved the way towards manufacturing a class of designer nanomaterials with properties precisely tailored by the nanoparticles and their interactions down to atomic scales. Despite the tremendous progress being made so far, multiple challenges have prevented the broader applications and impacts of the digital manufacturing technologies. This review features cutting-edge research in the development of some of the most advanced digital manufacturing methods. We focus on outlining major challenges in the field and providing our perspectives on the future research and development directions.

All-optical reconfigurable chiral meta-molecules.

Chirality is a ubiquitous phenomenon in the natural world. Many biomolecules without inversion symmetry such as amino acids and sugars are chiral molecules. Measuring and controlling molecular chirality at a high precision down to the atomic scale are highly desired in physics, chemistry, biology, and medicine, however, have remained challenging. Herein, we achieve all-optical reconfigurable chiral meta-molecules experimentally using metallic and dielectric colloidal particles as artificial atoms or building blocks to serve at least two purposes. One is that the on-demand meta-molecules with strongly enhanced optical chirality are well-suited as substrates for surface-enhanced chiroptical spectroscopy of chiral molecules and as active components in optofluidic and nanophotonic devices. The other is that the bottom-up-assembled colloidal meta-molecules provide microscopic models to better understand the origin of chirality in the actual atomic and molecular systems.

Opto-Thermophoretic Attraction, Trapping, and Dynamic Manipulation of Lipid Vesicles.

Lipid vesicles are important biological assemblies, which are critical to biological transport processes, and vesicles prepared in the lab are a workhorse for studies of drug delivery, protein unfolding, biomolecular interactions, compartmentalized chemistry, and stimuli-responsive sensing. The current method of using optical tweezers for holding lipid vesicles in place for single-vesicle studies suffers from limitations such as high optical power, rigorous optics, and small difference in the refractive indices of vesicles and water. Herein, we report the use of plasmonic heating to trap vesicles in a temperature gradient, allowing long-range attraction, parallel trapping, and dynamic manipulation. The capabilities and limitations with respect to thermal effects on vesicle structure and optical spectroscopy are discussed. This simple approach allows vesicle manipulation using down to 3 orders of magnitude lower optical power and at least an order of magnitude higher trapping stiffness per unit power than traditional optical tweezers while using a simple optical setup. In addition to the benefit provided by the relaxation of these technical constraints, this technique can complement optical tweezers to allow detailed studies on thermophoresis of optically trapped vesicles and effects of locally generated thermal gradients on the physical properties of lipid vesicles. Finally, the technique itself and the large-scale collection of vesicles have huge potential for future studies of vesicles relevant to detection of exosomes, lipid-raft formation, and other areas relevant to the life sciences.

Highly Efficient Photoelectrochemical Water Splitting from Hierarchical WO3/BiVO4 Nanoporous Sphere Arrays.

Nanoarchitecture of bismuth vanadate (BiVO4) photoanodes for effectively increasing light harvesting efficiency and simultaneously achieving high charge separation efficiency is the key to approaching their theoretic performance of solar-driven water splitting. Here, we developed hierarchical BiVO4 nanoporous sphere arrays, which are composed of small nanoparticles and sufficient voids for offering high capability of charge separation. Significantly, multiple light scattering in the sphere arrays and voids along with the large effective thickness of the BiVO4 photoanode induce efficient light harvesting. In addition, attributed to ultrathin two-dimensional Bi2WO6 nanosheets as the precursor, the synergy of various enhancement strategies including WO3/BiVO4 nanojunction formation, W-doping, and oxygen vacancy creation can be directly incorporated into such a unique hierarchical architecture during the one-step synthesis of BiVO4 without complex pre- or post-treatment. The as-obtained photoanode exhibits a water splitting photocurrent of 5.5 mA cm-2 at 1.23 V versus RHE under 1-sun illumination, among the best values reported up-to-date in the field.

Photoswitchable Rabi Splitting in Hybrid Plasmon-Waveguide Modes.

Rabi splitting that arises from strong plasmon-molecule coupling has attracted tremendous interests. However, it has remained elusive to integrate Rabi splitting into the hybrid plasmon-waveguide modes (HPWMs), which have advantages of both subwavelength light confinement of surface plasmons and long-range propagation of guided modes in dielectric waveguides. Herein, we explore a new type of HPWMs based on hybrid systems of Al nanodisk arrays covered by PMMA thin films that are doped with photochromic molecules and demonstrate the photoswitchable Rabi splitting with a maximum splitting energy of 572 meV in the HPWMs by controlling the photoisomerization of the molecules. Through our experimental measurements combined with finite-difference time-domain (FDTD) simulations, we reveal that the photoswitchable Rabi splitting arises from the switchable coupling between the HPWMs and molecular excitons. By harnessing the photoswitchable Rabi splitting, we develop all-optical light modulators and rewritable waveguides. The demonstration of Rabi splitting in the HPWMs will further advance scientific research and device applications of hybrid plasmon-molecule systems.

Bubble-Pen Lithography.

Current lithography techniques, which employ photon, electron, or ion beams to induce chemical or physical reactions for micro/nano-fabrication, have remained challenging in patterning chemically synthesized colloidal particles, which are emerging as building blocks for functional devices. Herein, we develop a new technique - bubble-pen lithography (BPL) - to pattern colloidal particles on substrates using optically controlled microbubbles. Briefly, a single laser beam generates a microbubble at the interface of colloidal suspension and a plasmonic substrate via plasmon-enhanced photothermal effects. The microbubble captures and immobilizes the colloidal particles on the substrate through coordinated actions of Marangoni convection, surface tension, gas pressure, and substrate adhesion. Through directing the laser beam to move the microbubble, we create arbitrary single-particle patterns and particle assemblies with different resolutions and architectures. Furthermore, we have applied BPL to pattern CdSe/ZnS quantum dots on plasmonic substrates and polystyrene (PS) microparticles on two-dimensional (2D) atomic-layer materials. With the low-power operation, arbitrary patterning and applicability to general colloidal particles, BPL will find a wide range of applications in microelectronics, nanophotonics, and nanomedicine.

Orthogonal and parallel lattice plasmon resonance in core-shell SiO(2)/Au nanocylinder arrays.

Height induced coupling behavior between the plasmonic modes and diffraction orders were studied in the core-shell SiO(2)/Au nanocylinder arrays (NCAs) using finite difference time domain (FDTD) simulations. New lattice plasmon modes (LPMs) are observed in the structures with high aspect ratio. Specifically, parallel coupling between the plasmonic modes and diffraction orders is obtained here, which shows different coupling behavior from orthogonal LPMs. Electromagnetic (EM) field distributions indicate that horizontal propagation of the magnetic or electric field component is responsible for the generation of these orthogonal and parallel LPMs, respectively. Radiative loss could be effectively suppressed when the height increases. This is important for the applications of fluorescence enhancement and nano laser. Further studies confirm that the LPMs associated with the superstrate diffraction orders could be well maintained even when the Au coating is imperfect. The interference from the substrate associated LPMs could be eliminated by cutting off the corresponding diffraction waves by inducing a Si(3)N(4) substrate. This study of coupling behavior in the core-shell NCAs enables a novel route to design and optimize the LPMs for applications of bio-sensing and nano laser.

Multiple plasmonic-photonic couplings in the Au nanobeaker arrays: enhanced robustness and wavelength tunability.

Diffractive coupling in the plasmonic nanoparticle arrays introduces the collective plasmon resonances with high scattering efficiency and narrow linewidth. However, the collective plasmon resonances can be suppressed when the arrays are supported on the solid-state substrates with different superstrates because of the different dispersion relations between the substrate and the superstrate. Herein, we develop a general concept which seeks to synergize the subnanoparticle engineering of "hot spots" with the far-field coupling behavior, for the versatile control of plasmonic-photonic couplings in an asymmetric environment. To demonstrate our concept, we choose as an example the Au nanobeaker arrays (NBAs), which are the conformally coated Au thin layers on the interior sidewalls and bottoms of nanohole arrays in SiO2 substrates. Using the finite-difference time-domain simulations, we show that engineering the plasmonic "hot spots" in the NBAs by simply controlling the depth-to-diameter aspect ratio of individual units enables multiple plasmonic-photonic couplings in an asymmetric environment. These couplings are robust with a wide range of resonance wavelengths from visible to infrared. Furthermore, the angle-dependent transmission spectra of the arrays reveal a transition from band-edge to propagating state for the orthogonal coupling and a splitting of diffraction waves in the parallel coupling. The proposed NBAs will find enhanced applications in plasmonic lasers and biosensing.

Lattice plasmon resonance in core-shell SiO2/Au nanocylinder arrays.

Core-shell SiO2/Au nanocylinder arrays (NCAs) are studied using finite-difference time-domain simulations. The increase of height induces new surface plasmon resonances along the nanocylinders, i.e., dipole and quadrupole modes. Orthogonal coupling between superstrate diffraction order and the height-induced dipole mode is observed, which could achieve a well-defined lattice plasmon mode even for smaller NCAs in asymmetric environments. Electromagnetic field distribution has been employed to determine the coupling origin. Radiative loss could also be effectively suppressed in these core-shell NCAs, indicating the possibility of future applications in fluorescence enhancement and nanolasers.

Optofluidic crystallithography for directed growth of single-crystalline halide perovskites.

Crystallization is a fundamental phenomenon which describes how the atomic building blocks such as atoms and molecules are arranged into ordered or quasi-ordered structure and form solid-state materials. While numerous studies have focused on the nucleation behavior, the precise and spatiotemporal control of growth kinetics, which dictates the defect density, the micromorphology, as well as the properties of the grown materials, remains elusive so far. Herein, we propose an optical strategy, termed optofluidic crystallithography (OCL), to solve this fundamental problem. Taking halide perovskites as an example, we use a laser beam to manipulate the molecular motion in the native precursor environment and create inhomogeneous spatial distribution of the molecular species. Harnessing the coordinated effect of laser-controlled local supersaturation and interfacial energy, we precisely steer the ionic reaction at the growth interface and directly print arbitrary single crystals of halide perovskites of high surface quality, crystallinity, and uniformity at a high printing speed of 102 µm s-1. The OCL technique can be potentially extended to the fabrication of single-crystal structures beyond halide perovskites, once crystallization can be triggered under the laser-directed local supersaturation.

Indirect to direct band gap transition in ultra-thin silicon films.

Free standing silicon layers undergo a transition from indirect to direct band gap semiconductor, which predicts a new possible way in silicon band gap engineering. The thickness and crystal orientation of the exposed surface are crucial. Our simulations reveal that the (100) films with thickness of ∼1.05 nm and (110) films with thickness of ∼1.14 nm could maintain the direct band gap structure. However, the (111) films always show indirect band gap structure even if the monolayer is constructed. The electron states density calculations were also carried out and the transition of the band gap structure is considered to be determined by the quantum confinement and surface termination conditions. The momentum matrix element calculations were also carried out, approving the effective direct band gap transitions for these ultra-thin films.

Non-Invasive and Minute-Frequency 3D Tomographic Imaging Enabling Long-Term Spatiotemporal Observation of Single Cell Fate.

Non-invasive and rapid imaging technique at subcellular resolution is significantly important for multiple biological applications such as cell fate study. Label-free refractive-index (RI)-based 3D tomographic imaging constitutes an excellent candidate for 3D imaging of cellular structures, but its full potential in long-term spatiotemporal cell fate observation is locked due to the lack of an efficient integrated system. Here, a long-term 3D RI imaging system incorporating a cutting-edge white light diffraction phase microscopy module with spatiotemporal stability, and an acoustofluidic device to roll and culture single cells in a customized live cell culture chamber is reported. Using this system, 3D RI imaging experiments are conducted for 250 cells and demonstrate efficient cell identification with high accuracy. Importantly, long-term and frequency-on-demand 3D RI imaging of K562 and MCF-7 cancer cells reveal different characteristics during normal cell growth, drug-induced cell apoptosis, and necrosis of drug-treated cells. Overall, it is believed that the proposed 3D tomographic imaging technique opens up a new avenue for visualizing intracellular structures and will find many applications such as disease diagnosis and nanomedicine.

3D printing of inorganic nanomaterials by photochemically bonding colloidal nanocrystals.

3D printing of inorganic materials with nanoscale resolution offers a different materials processing pathway to explore devices with emergent functionalities. However, existing technologies typically involve photocurable resins that reduce material purity and degrade properties. We develop a general strategy for laser direct printing of inorganic nanomaterials, as exemplified by more than 10 semiconductors, metal oxides, metals, and their mixtures. Colloidal nanocrystals are used as building blocks and photochemically bonded through their native ligands. Without resins, this bonding process produces arbitrary three-dimensional (3D) structures with a large inorganic mass fraction (~90%) and high mechanical strength. The printed materials preserve the intrinsic properties of constituent nanocrystals and create structure-dictated functionalities, such as the broadband chiroptical responses with an anisotropic factor of ~0.24 for semiconducting cadmium chalcogenide nanohelical arrays.

High-temperature flexible WSe2 photodetectors with ultrahigh photoresponsivity.

The development of high-temperature photodetectors can be beneficial for numerous applications, such as aerospace engineering, military defence and harsh-environments robotics. However, current high-temperature photodetectors are characterized by low photoresponsivity (<10 A/W) due to the poor optical sensitivity of commonly used heat-resistant materials. Here, we report the realization of h-BN-encapsulated graphite/WSe2 photodetectors which can endure temperatures up to 700 °C in air (1000 °C in vacuum) and exhibit unconventional negative photoconductivity (NPC) at high temperatures. Operated in NPC mode, the devices show a photoresponsivity up to 2.2 × 106 A/W, which is ~5 orders of magnitude higher than that of state-of-the-art high-temperature photodetectors. Furthermore, our devices demonstrate good flexibility, making it highly adaptive to various shaped surfaces. Our approach can be extended to other 2D materials and may stimulate further developments of 2D optoelectronic devices operating in harsh environments.

Direct Patterning of Colloidal Nanocrystals via Thermally Activated Ligand Chemistry.

Precise patterning with microscale lateral resolution and widely tunable heights is critical for integrating colloidal nanocrystals into advanced optoelectronic and photonic platforms. However, patterning nanocrystal layers with thickness above 100 nm remains challenging for both conventional and emerging direct photopatterning methods, due to limited light penetration depths, complex mechanical and chemical incompatibilities, and others. Here, we introduce a direct patterning method based on a thermal mechanism, namely, the thermally activated ligand chemistry (or TALC) of nanocrystals. The ligand cross-linking or decomposition reactions readily occur under local thermal stimuli triggered by near-infrared lasers, affording high-resolution and nondestructive patterning of various nanocrystals under mild conditions. Patterned quantum dots fully preserve their structural and photoluminescent quantum yields. The thermal nature allows for TALC to pattern over 10 µm thick nanocrystal layers in a single step, far beyond those achievable in other direct patterning techniques, and also supports the concept of 2.5D patterning. The thermal chemistry-mediated TALC creates more possibilities in integrating nanocrystal layers in uniform arrays or complex hierarchical formats for advanced capabilities in light emission, conversion, and modulation.

3D nanoprinting of semiconductor quantum dots by photoexcitation-induced chemical bonding.

Three-dimensional (3D) laser nanoprinting allows maskless manufacturing of diverse nanostructures with nanoscale resolution. However, 3D manufacturing of inorganic nanostructures typically requires nanomaterial-polymer composites and is limited by a photopolymerization mechanism, resulting in a reduction of material purity and degradation of intrinsic properties. We developed a polymerization-independent, laser direct writing technique called photoexcitation-induced chemical bonding. Without any additives, the holes excited inside semiconductor quantum dots are transferred to the nanocrystal surface and improve their chemical reactivity, leading to interparticle chemical bonding. As a proof of concept, we printed arbitrary 3D quantum dot architectures at a resolution beyond the diffraction limit. Our strategy will enable the manufacturing of free-form quantum dot optoelectronic devices such as light-emitting devices or photodetectors.