Reconfigurable, Reversible, and Redefinable Deformation of GO Based on Quantum-Confined-Superfluidics Effect.

Graphene oxide (GO) films with natural "quantum-confined-superfluidics" (QSF) channels for moisture actuation have emerged as a smart material for actuators and soft robots. However, programming the deformation of GO by engineering QSF nanochannels around 1 nm is extremely challenging. Herein, we report the reconfigurable, reversible, and redefinable deformation of GO under moisture actuation by tailoring QSF channels via moisture-assisted strain-induced wrinkling (MSW). The shape fixity ratio of a general GO film can reach ∼84% after the MSW process, and the shape recovery ratio is ∼83% at room temperature under moisture actuation. The flexible shaping and deformation abilites, as well as the self-healing property of GO make it possible to fabricate soft robots using GO. Besides, as a proof-of-concept, passive electronics and soft robots capable of crawling, turning, switching circuit, and automatic somersault are demonstrated. With unique shaping and deformation abilities, GO may bring great implications for future soft robotics.

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.

Ag nanoparticle ink coupled with graphene oxide cellulose paper: a flexible and tunable SERS sensing platform.

Surface-enhanced Raman scattering (SERS) is highly promising for ultra-sensitive detection in a series of applications. Although extensive advances have been achieved in SERS technologies, the preparation of highly efficient SERS substrates still suffers from several limitations, including complex preparation procedures, high cost, and instability for long time storage. To address these problems, we report a novel, to the best of our knowledge, SERS platform that combines graphene oxide (GO) and cellulose composite paper with colloidal silver nanoparticle (Ag NP) ink. As an efficient substrate, the GO and cellulose composite paper that features hierarchical micro-nanostructures and improved interaction with target molecules can be fabricated on a large scale, and the Ag NP ink can be well stored, avoiding being oxidized in ambient conditions. In this way, our SERS platform not only reduces the cost, but also improved the stability. The sensitivity, reproducibility, and tunable SERS detection performance were evaluated using rhodamine 6G as probing molecules. To demonstrate the capability of our SERS platform in practical analysis, the SERS spectra of two monosodium salt solutions of different concentrations have been collected. The SERS platform has revealed great potential for practical application of SERS technologies.

Laser fabrication of graphene-based electrothermal actuators enabling predicable deformation.

Electrothermal actuators (ETAs) that can convert electric energy into mechanical works have been extensively studied for their great potential in artificial muscles and robotics. However, the production of ETAs that enable complex and predictable deformation is still challenging. In this Letter, an ETA based on reduced graphene oxide (RGO) and polyethylene (PE) bimorph is developed through a facile laser-scribing method. Since the laser-scribing technology permits flexible patterning, conductive RGO electrodes with complex circuit patterns can be readily produced on a thermally active PE film, forming an ETA capable of fast and reversible deformation. In addition, the laser-scribed ETA demonstrated orientation-defined bending performance, enabling more sophisticated deformation control. The laser scribing of graphene oxide has opened up a new way to produce ETAs towards cutting-edge applications such as soft robotics and intelligent systems.

Hierarchically structuring and synchronous photoreduction of graphene oxide films by laser holography for supercapacitors.

Herein, we report a simple laser holography technology for hierarchically structuring and synchronous photoreduction of graphene oxides (GO), toward the development of efficient graphene-based electrodes for supercapacitor applications in cost effectively manners. Hierarchical micro-nanostructures, formed due to laser treatment induced photoreduction and ablation effect. Interestingly, both the morphology and reduction degree of the laser holography reduced GO (LHRGO) show strong dependence on the laser intensity, providing the feasibility for controlling the micro-nanostructures, chemical composition, and the conductivity of the graphene electrodes. Furthermore, the supercapacitors based on LHRGO show higher capacitance values and better electrochemical performance compared to that based on thermal reduced GO (TRGO) of same reduction level. Photoredution and micro-nanostructuring of GO using laser holography may hold great promise for production of effective carbon-based electrodes towards practical applications in energy storage devices.

Kraft Mesh Origami for Efficient Oil-Water Separation.

Inspired from fish scales that exhibit unique underwater superoleophobicity, artificial porous membranes featuring similar wettability have been successfully developed for oil-water separation. However, most of the superoleophobic meshes are workable only for underwater oil/water separation and become disabled in air. In this article, we reported the facile fabrication of underwater superoleophobic kraft mesh and demonstrated efficient oil-water separation using kraft mesh origamis. Kraft paper that features porosity, natural hydrophilicity, and relatively high elasticity and tear resistance has been found to be an ideal candidate for developing underwater superoleophobic origami. Direct laser drilling has been employed to make microhole arrays on the kraft paper, forming a flexible mesh. The hydrophilic nature and the hierarchical microstructures that consist of microhole arrays and porous microfiber networks make the resultant kraft mesh superoleophobic underwater, enabling oil-water separation. More importantly, the kraft mesh can retain a large amount of water (2.5 times its weight under dry conditions) owing to its porous and hydrophilic structure. Thus, the wet kraft mesh became a slippery surface for oil droplets when it was taken out of the water. This unique feature makes it possible to directly fish out oil droplets from water using a simple kraft mesh origami. Direct laser drilling of paper mesh for flexible origami may open up a new route to the rational design and fabrication of oil-water separation devices.

Femtosecond laser direct writing of ion exchangeable multifunctional microstructures.

We report on the fabrication of ion exchangeable microstructures by femtosecond laser direct writing of an ion exchange photopolymer, poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS). The resultant microstructures are negatively charged in aqueous solution, and can adsorb positively charged species, such as metal ions, nanoparticles, and proteins by electrostatic interaction, forming functional components for chip functionalization. In addition, it is possible to modify the microstructures with positively charged species that make the microstructures sensitive to negatively charged species. As a typical example, a crossed 3D microvessel functionalized with antibodies was fabricated, which reveals great potential for organ-on-a-chip systems. The fabrication of ion exchangeable microstructures holds great promise for flexible chip functionalization.

Intense Femtosecond Laser-Mediated Electrical Discharge Enables Preparation of Amorphous Nickel Phosphide Nanoparticles.

Reported here is a high-efficiency preparation method of amorphous nickel phosphide (Ni-P) nanoparticles by intense femtosecond laser irradiation of nickel sulfate and sodium hypophosphite aqueous solution. The underlying mechanism of the laser-assisted preparation was discussed in terms of the breaking of chemical bond in reactants via highly intense electric field discharge generated by the intense femtosecond laser. The morphology and size of the nanoparticles can be tuned by varying the reaction parameters such as ion concentration, ion molar ratio, laser power, and irradiation time. X-ray diffraction and transmission electron microscopy results demonstrated that the nanoparticles were amorphous. Finally, the thermogravimetric-differential thermal analysis experiment verified that the as-synthesized noncrystalline Ni-P nanoparticles had an excellent catalytic capability toward thermal decomposition of ammonium perchlorate. This strategy of laser-mediated electrical discharge under such an extremely intense field may create new opportunities for the decomposition of molecules or chemical bonds that could further facilitate the recombination of new atoms or chemical groups, thus bringing about new possibilities for chemical reaction initiation and nanomaterial synthesis that may not be realized under normal conditions.

Wet-etching-assisted femtosecond laser holographic processing of a sapphire concave microlens array.

We report rapid and mask-free fabrication of a sapphire concave microlens array by a combined method of femtosecond laser holographic processing and wet etching. The method features high fabrication efficiency, as crater arrays can be created on sapphire through a parallel processing manner, and the subsequent wet etching facilitates the formation of microlens arrays with a smooth surface. More importantly, the size and spacing of the concave microlenses can be well tuned by varying the distance of craters and etching time. Two types of microlens arrays with a spacing of 25 and 40 µm have been successfully fabricated, both of which showed good imaging performance. This method holds great promise for developing sapphire-based micro-optical components.

Facile fabrication of flexible graphene FETs by sunlight reduction of graphene oxide.

We reported here a facile fabrication of flexible graphene-based field effect transistors (FETs) by sunlight reduction of graphene oxide (GO) as channel material. As a mask-free and chemical-free method, sunlight photoreduction of GO without the use of any complex equipments is simple and green. The resultant FET demonstrated excellent electrical properties (e.g., an optimized Ion/Ioff ratio of 111, hole mobility of 0.17 cm2 V-1 s-1), revealing great potential for development of flexible microelectrics. Additionally, since the reduced GO channel could be fabricated by sunlight treatment between two pre-patterned electrodes, the process features post-fabrication capability, which makes it possible to integrate graphene-based devices with given device structures.

Surface and Interface Engineering of Graphene Oxide Films by Controllable Photoreduction.

We report herein the engineering of the surface/interface properties of graphene oxide (GO) films by controllable photoreduction treatment. In our recent works, typical photoreduction processes, including femtosecond laser direct writing (FsLDW), laser holographic lithography, and controllable UV irradiation, have been employed to make conductive reduced graphene oxide (RGO) microcircuits, hierarchical RGO micro-nanostructures with both superhydrophobicity and structural color, as well as moisture-responsive GO/RGO bilayer structures. Compared with other reduction protocols, for instance, chemical reduction and thermal annealing, the photoreduction strategy shows distinct advantages, such as mask-free patterning, chemical-free modification, controllable reduction degree, and environmentally friendly processing. These works indicate that the surface and interface engineering of GO through controllable photoreduction of GO holds great promise for the development of various graphene-based microdevices.

Controllable assembly of silver nanoparticles induced by femtosecond laser direct writing.

We report controllable assembly of silver nanoparticles (Ag NPs) for patterning of silver microstructures. The assembly is induced by femtosecond laser direct writing (FsLDW). A tightly focused femtosecond laser beam is capable of trapping and driving Ag NPs to form desired micropatterns with a high resolution of ∼190 nm. Taking advantage of the 'direct writing' feature, three microelectrodes have been integrated with a microfluidic chip; two silver-based microdevices including a microheater and a catalytic reactor have been fabricated inside a microfluidic channel for chip functionalization. The FsLDW-induced programmable assembly of Ag NPs may open up a new way to the designable patterning of silver microstructures toward flexible fabrication and integration of functional devices.

Reconfigurable Microlens Array Enables Tunable Imaging Based on Shape Memory Polymers.

Microlens arrays (MLAs) with a tunable imaging ability are core components of advanced micro-optical systems. Nevertheless, tunable MLAs generally suffer from high power consumption, an undeformable rigid body, large and complex systems, or limited focal length tunability. The combination of reconfigurable smart materials with MLAs may lead to distinct advantages including programmable deformation, remote manipulation, and multimodal tunability. However, unlike photopolymers that permit flexible structuring, the fabrication of tunable MLAs and compound eyes (CEs) based on transparent smart materials is still rare. In this work, we report reconfigurable MLAs that enable tunable imaging based on shape memory polymers (SMPs). The smart MLAs with closely packed 200 × 200 microlenses (40.0 µm in size) are fabricated via a combined technology that involves wet etching-assisted femtosecond laser direct writing of MLA templates on quartz, soft lithography for MLA duplication using SMPs, and the mechanical heat setting for programmable reconfiguration. By stretching or squeezing the shape memory MLAs at the transition temperature (80 °C), the size, profiles, and spatial distributions of the microlenses can be programmed. When the MLA is stretched from 0 to 120% (area ratio), the focal length is increased from 116 to 283 µm. As a proof of concept, reconfigurable MLAs and a 3D CE with a tunable field of view (FOV, 160-0°) have been demonstrated in which the thermally triggered shape memory deformation has been employed for tunable imaging. The reconfigurable MLAs and CEs with a tunable focal length and adjustable FOV may hold great promise for developing smart micro-optical systems.

Hyper-branched CdTe nanostructures based on the self-assembling of quantum dots and their optical properties.

As the priority of interconnects and active components in nanoscale optical and electronic devices, three-dimensional hyper-branched nanostructures came into focus of research. Recently, a novel crystallization route, named as "nonclassical crystallization," has been reported for three-dimensional nanostructuring. In this process, Quantum dots are used as building blocks for the construction of the whole hyper-branched structures instead of ions or single-molecules in conventional crystallization. The specialty of these nanostructures is the inheritability of pristine quantum dots' physical integrity because of their polycrystalline structures, such as quantum confinement effect and thus the luminescence. Moreover, since a longer diffusion length could exist in polycrystalline nanostructures due to the dramatically decreased distance between pristine quantum dots, the exciton-exciton interaction would be different with well dispersed quantum dots and single crystal nanostructures. This may be a benefit for electron transport in solar cell application. Therefore, it is very necessary to investigate the exciton-exciton interaction in such kind of polycrystalline nanostructures and their optical properites for solar cell application. In this research, we report a novel CdTe hyper-branched nanostructures based on self-assembly of CdTe quantum dots. Each branch shows polycrystalline with pristine quantum dots as the building units. Both steady state and time-resolved spectroscopy were performed to investigate the properties of carrier transport. Steady state optical properties of pristine quantum dots are well inherited by formed structures. While a suppressed multi-exciton recombination rate was observed. This result supports the percolation of carriers through the branches' network.

Photothermal responsive slippery surfaces based on laser-structured graphene@PVDF composites.

Photothermal responsive slippery surfaces with switchable superwettability are promising in the fields of biomedicine, self-cleaning, anti-corrosion, and lab-on-a-chip systems. However, the development of a light switchable slippery surface that combines high-performance photothermal materials with hierarchical microstructures of special orientation remains challenging, which limits the applications in anisotropic droplet manipulation. Herein, we demonstrate a photothermal responsive slippery surface based on laser-structured graphene and polyvinylidene difluoride composites (L-G@PVDF) for controllable droplet manipulation. The L-G@PVDF film exhibits high light absorption (∼95.4%) in the visible and NIR region. After lubricating with paraffin, the resultant surface shows excellent self-healing ability and light-responsive wettability change due to the photothermal effect of L-G@PVDF and the hot melting effect of paraffin. Additionally, by introducing anisotropic grooved structures, the paraffin-infused L-G@PVDF surface displays anisotropic wettability that further affects droplet manipulation under light irradiation. Also, the photothermal responsive slippery property endows the paraffin-infused L-G@PVDF surface with excellent anti-frosting and de-icing capability. Moreover, the smart paraffin-infused L-G@PVDF surface can be combined with a microfluidics chip for light-driven automatic sampling. This study offers insight into the rational design of photothermal responsive slippery surfaces for controllable droplet manipulation.

Multicoating Nanoarchitectonics for Facile Preparation of Multi-Responsive Paper Actuators.

Stimuli-responsive actuators (SRAs) that can harvest environmental energies and convert them to mechanical works without additional energy-supplying systems have revealed great potential for robotic applications. However, at present, the practical usage of SRAs is significantly limited due to the problems with respect to solo responsiveness, simple deformation, and the difficulties for large-scale and cost-effective production. In this paper, multi-responsive paper actuators with multicoating nanoarchitectonics that enable complex deformation have been fabricated through a very simple painting process on common papers. The resultant paper actuator permits large-scale and low-cost production (A4 size: ∼0.5 dollar). The paper actuators that consist of a paper/graphite/polydimethylsiloxane sandwich structure can be actuated by multi-form stimuli, including moisture, temperature, light, and volatile organic compounds. More importantly, the bending deformation of the paper actuators can be further programmed by controlling the pencil drawing orientation, providing the feasibility of performing more complex deformations. Several multi-responsive paper actuators, including organic compound-responsive smart devices working in the liquid environment, moisture-enabled terrestrial crawling actuator, and a light-responsive attitude-control actuator integrated with an airplane model, have been demonstrated. The development of multi-responsive yet cost-effective paper actuators may hold great promise for a wide range of practical applications, for instance, soft micro-electromechanical systems, lab-on-a-chip systems, smart homes, and robotics.

Miniature optoelectronic compound eye camera.

Inspired by insect compound eyes (CEs) that feature unique optical schemes for imaging, there has recently been growing interest in developing optoelectronic CE cameras with comparable size and functions. However, considering the mismatch between the complex 3D configuration of CEs and the planar nature of available imaging sensors, it is currently challenging to reach this end. Here, we report a paradigm in miniature optoelectronic integrated CE camera by manufacturing polymer CEs with 19~160 logarithmic profile ommatidia via femtosecond laser two-photon polymerization. In contrast to µ-CEs with spherical ommatidia that suffer from defocusing problems, the as-obtained µ-CEs with logarithmic ommatidia permit direct integration with a commercial CMOS detector, because the depth-of-field and focus range of all the logarithmic ommatidia are significantly increased. The optoelectronic integrated µ-CE camera enables large field-of-view imaging (90°), spatial position identification and sensitive trajectory monitoring of moving targets. Moreover, the miniature µ-CE camera can be integrated with a microfluidic chip and serves as an on-chip camera for real-time microorganisms monitoring. The insect-scale optoelectronic µ-CE camera provides a practical route for integrating well-developed planar imaging sensors with complex micro-optics elements, holding great promise for cutting-edge applications in endoscopy and robot vision.

Heterogeneous self-healing assembly of MXene and graphene oxide enables producing free-standing and self-reparable soft electronics and robots.

Self-healing materials (SHMs) with unique mechanical and electronic properties are promising for self-reparable electronics and robots. However, the self-healing ability of emerging two-dimensional (2D) materials, for instance, MXenes, has not been systematically investigated, which limits their applications in self-healing electronics. Herein, we report the homogeneous self-healing assembly (homo-SHA) of MXene and the heterogeneous self-healing assembly (hetero-SHA) of MXene and graphene oxide (GO) under moisture treatments. The self-healing mechanism has been attributed to the hydration induced interlayer swelling of MXene and GO and the recombination of hydrogen bond networks after water desorption. The multiform hetero-SHA of MXene and GO not only enables facile fabrication of free-standing soft electronics and robots, but also endows the resultant devices with damage-healing properties. As proof-of-concept demonstrations, free-standing soft electronic devices including a generator, a humidity sensor, a pressure sensor, and several robotic devices have been fabricated. The hetero-SHA of MXene and GO is simple yet effective, and it may pioneer a new avenue to develop miniature soft electronics and robots based on 2D materials.

A SERS-active microfluidic device with tunable surface plasmon resonances.

A surface-enhanced Raman scattering (SERS)-active microfluidic device with tunable surface plasmon resonances is presented here. It is constructed by silver grating substrates prepared by two-beam laser interference of photoresists and subsequent metal evaporation coating, as well as PDMS microchannel derived from soft lithography. By varying the period of gratings from 200 to 550 nm, surface plasmon resonances (SPRs) from the metal gratings could be tuned in a certain range. When the SPRs match with the Raman excitation line, the highest enhancement factor of 2×10(7) is achieved in the SERS detection. The SERS-active microchannel with tunable SPRs exhibits both high enhancement factor and reproducibility of SERS signals, and thus holds great promise for applications of on-chip SERS detection.

Solvothermal synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces.

Reported here is a facile synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces. Taking this nanoporous polymer as a media, superhydrophobicity is rapidly imparted onto three typical kinds of substrates, including paper, transparent polydimethylsiloxane (PDMS), and finger skin. Quantitative characterization showed that the adhesion between the water droplet and polymer-coated substrates decreased significantly compared to that on the original surface, further indicating the effective wetting mode transformation. The nanoporous polymer coating would open a new door for facile, rapid, safe, and larger scale fabrication of superhydrophobic surfaces on general substrates.