Portable Triboelectric Electrostatic Tweezer for External Manipulation of Droplets within a Closed Femtosecond Laser-Treated Superhydrophobic System.

Controllable droplet manipulation has diverse applications; however, limited methods exist for externally manipulating droplets in confined spaces. Herein, we propose a portable triboelectric electrostatic tweezer (TET) by integrating electrostatic forces with a superhydrophobic surface that can even manipulate droplets in an enclosed space. Electrostatic induction causes the droplet to be subjected to an electrostatic force in an electrostatic field so that the droplet can be moved freely with the TET on a superhydrophobic platform. Characterized by its high precision, flexibility, and robust binding strength, TET can manipulate droplets under various conditions and achieve a wide range of representative fluid applications such as droplet microreactors, precise self-cleaning, cargo transportation, the targeted delivery of chemicals, liquid sorting, soft droplet robotics, and cell labeling. Specifically, TET demonstrated the ability to manipulate internal droplets from the outside of a closed system, such as performing cell labeling experiments within a sealed Petri dish without opening the culture system.

Femtosecond laser hybrid fabrication of a 3D microfluidic chip for PCR application.

Microfluidic chips have gradually become a focus of scientific research. However, the fabrication of key functional components in microfluidic chips is always limited by the existing processing methods. The microfluidic chip is difficult to be three-dimensional (3D) and integrated. In response to the key problems of 3D integrated microfluidic chip fabrication, this paper presents a hybrid method for fabricating a microfluidic chip integrated 3D microchannels and metal microstructures by femtosecond laser wet etch technology and liquid metal injection. The integrated microfluidic chip fabricated by this method is expected to be applied to the core reaction unit of integrated PCR devices.

Magnetically Controllable Isotropic/Anisotropic Slippery Surface for Flexible Droplet Manipulation.

Controllable wetting surfaces play a significant role in numerous applications such as smart liquid manipulation, lab-on-a-chip, drug delivery, liquid robot, and so on. A novel type of magnetically controllable isotropic/anisotropic slippery surface was prepared by femtosecond laser ablation. The slippery liquid-infused porous surface (SLIPS) can be switched between an isotropic smooth state and an anisotropic groove state by the magnetic field. The relationship between the sliding property of the SLIPS and the magnetic flux density, water droplet volume, microgroove width, and microgroove height are systematically studied. Passively flexible movement on the isotropic SLIPS and actively directional movement on the anisotropic SLIPS of water droplets were realized. This work provides a fresh understanding of the controllable isotropic/anisotropic SLIPS and reveals great potential in versatile applications which are related to magnetically controllable smart liquid manipulation.

Underwater superoleophobic and anti-oil microlens array prepared by combing femtosecond laser wet etching and direct writing techniques.

As an important micro-optical device, microlens array (MLA) also has broad applications in aqueous environment apart from atmosphere, such as bioscience research, ocean exploration, and microfluidic systems. However, the surface of the normal MLA is easily polluted by oil contaminations when the MLA is practically applied in a water medium, leading to the loss of its optical imaging ability. Herein, we fabricated a functional MLA with underwater anti-oil and self-cleaning abilities by combining the femtosecond laser wet etching (FLWE) and the femtosecond laser direct writing (FLDW) techniques. The as-prepared close-packed MLA is composed of 10000 single microlenses with the aperture diameter of 50 µm. The surface of each microlens is further textured with micro/nanoparticles. Clear and uniform images could be captured by using the resultant MLA in water, demonstrating great underwater imaging ability. The modulation transfer function value is larger than 0.6 at 55 lp/mm. In addition, the micro/nanostructures endow the as-fabricated MLA surface with underwater superoleophobicity and oil-repellent performance. Various oils can be repelled by the resultant MLA in water. Underwater 1,2-dichloroethane oil droplet on the textured MLA has a contact angle of 158.0 ± 0.5° and a sliding angle of 2.0 ± 0.2°. The underwater superoleophobic MLA also has good mechanical durability. The anti-oil and self-cleaning functions will broaden the applications of the MLA in ocean exploration, bioscience research, microfluidic system, and many underwater MLA-based systems.

Femtosecond Laser-Induced Underwater Superoleophobic Surfaces with Reversible pH-Responsive Wettability.

Wettability-switchable surfaces have become a research hotspot because they can exhibit different superwetting states. In this paper, the copper surfaces with pH-responsive underwater-oil wettability were prepared by femtosecond laser treatment and subsequent chemical modification. The resultant surfaces showed underwater superoleophobicity in alkaline solutions but quasi-superoleophilicity in acidic solutions. The contact angles of an underwater-oil droplet on the resultant surfaces could be reversibly tuned between 157° and 12° by changing the pH of aqueous solutions. Such switchable wettability is ascribed to the modification of the alkyl and carboxylic acids groups on the laser-structured surfaces. The as-prepared surfaces have both oil-resistance and oil-collection abilities by selectively showing underwater superoleophobicity and superoleophilicity. The smart surfaces with pH-responsive oil wettability will have important applications in controlling the oil behavior in water.

How To Obtain Six Different Superwettabilities on a Same Microstructured Pattern: Relationship between Various Superwettabilities in Different Solid/Liquid/Gas Systems.

A range of different superwettabilities were obtained on femtosecond laser-structured Al surfaces. The formation mechanism of each superwetting state is discussed in this paper. It is revealed that the underwater oil droplet and bubble wettabilities of a solid surface have a close relationship with its water wettability. The laser-induced hierarchical microstructures showed superhydrophilicity in air but showed superoleophobicity/superaerophobicity after immersion in water. When such microstructures were further modified with a low-surface-energy monolayer, the wettability of the resultant surface would turn to superhydrophobicity with ultralow water adhesion in air and superoleophilicity/superaerophilicity in water. The understanding of the relationship among the above-mentioned six different superwettabilities is highly important in the design of various superwetting microstructures, transforming the structures from one superwetting state to another state and better using the artificial superwetting materials.

Femtosecond Laser-Structured Underwater "Superpolymphobic" Surfaces.

In this work, the surfaces that repel liquid polydimethylsiloxane (PDMS) droplets in water were created by femtosecond laser treatment. We define this superwetting phenomenon as underwater "superpolymphobicity". The resultant underwater superpolymphobic silicon surface shows a contact angle of 159 ± 1° and a sliding angle of 1.5 ± 0.5° to liquid PDMS droplets in water. This underwater superpolymphobicity can be achieved on a wide range of hydrophilic materials, including semiconductors, glass, and metals. The adhesion between the liquid polymer and a solid substrate is effectively prevented by the underwater superpolymphobic microstructures. The underwater superpolymphobicity will have a great significance in designing the adhesion between the polymer and a solid substrate, controlling the shape of the cured polymer materials, as well as nearly all the applications based on the polymer materials.

Oil/water separation based on natural materials with super-wettability: recent advances.

The frequency of oil spills and the increasing amount of oily sewage not only cause serious water pollution as well as a lot of ecological problems but also result in huge economic losses. To address such problems, developing advanced technologies and materials for achieving efficient oil/water separation is a critical way and emerging as a hot research topic nowadays. Herein, we have reviewed the recent developments in oil/water separation by using superwetting porous materials, mainly focusing on natural materials. By using natural materials as examples, we show how to use superwetting porous materials to separate different mixtures of water and oil, including the inherent superwettability of the natural materials, separating method/process, and separation mechanism. Natural superwetting materials are usually low-cost and eco-friendly, and can be easily obtained, so oil/water separation based on natural materials has great promise to address the above-mentioned globally recognized oil contamination challenge. In addition, these natural examples seem more attractive to the general researcher who is new to this field as well as the expert and even the public, since natural materials look more interesting than artificial complex materials. We believe our review will help beginners better understand the significance, application value, mechanism and principle of oil/water separation by superwetting porous materials.

Superoleophobic surfaces.

Superoleophobicity is a phenomenon where the contact angles of various oil droplets with low surface tension on a solid surface are larger than 150°. In the past few years, there has been much growing interest in the design and application of superoleophobic surfaces. Such surfaces have great significance for both fundamental research and a variety of practical applications, including oil-repellent coatings, self-cleaning, oil/water separation, oil droplet manipulation, chemical shielding, anti-blocking, designing liquid microlens, oil capture, bioadhesion, guiding oil movement and floating on oil. Herein, we systematically summarize the recent developments of superoleophobic surfaces. This review focuses on the design, fabrication, characteristics, functions, and important applications of various superoleophobic surfaces. Although many significant advances have been achieved, superoleophobic surfaces are still in their "toddler stage" of development. The current challenges and future prospects of this fast-growing field of superoleophobicity are discussed.

Underwater Transparent Miniature "Mechanical Hand" Based on Femtosecond Laser-Induced Controllable Oil-Adhesive Patterned Glass for Oil Droplet Manipulation.

Development of underwater superoleophobic surfaces has captured the imagination of researchers because of their applications; especially, oil manipulation based on such surfaces has attracted much attention. Here, we show a simple and effective way to fabricate an underwater transparent miniature "mechanical hand" based on controllable oil-adhesive patterned glass using a femtosecond laser. The underwater oil-adhesive force of the patterned glasses that compose the "mechanical hand" device can be controlled from ultralow to ultrahigh by adjusting the ratio of the untreated flat glass area to the laser-ablated rough area. These surfaces also showed favorable transparency in water. Various oils such as chloroform, hexadecane, n-dodecane, decane, liquid paraffin, and petroleum ether were tested, and their repellency against the as-prepared surfaces in water medium was confirmed. Moreover, the "mechanical hand" was used to implement oil transportation, fusion, and rapid capture, which can be applied in the construction of microfluidic devices, in situ detectors, and bioreactors.

Lens-on-lens microstructures.

Microlenses with multiple focal lengths play an important role in three-dimensional imaging and the real-time detection of unconfined or fluctuating targets. In this Letter, we present a novel method of fabricating lens-on-lens microstructures (LLMs) using a two-step femtosecond laser wet etching process. A 3×3 LLM array was made with a diameter of 129.0 µm. The fabricated LLM has two focal lengths, 80.4 and 188.7 µm, showing excellent two-level focusing and imaging abilities. Its size and focal length can be controlled by adjusting laser power and etching time. Its surface roughness remains about 61 nm. This simple and efficient method for large-scale production of LLMs has potential applications in diverse optical systems.

Fabrication of large-area concave microlens array on silicon by femtosecond laser micromachining.

In this Letter, a novel fabrication of large-area concave microlens array (MLA) on silicon is demonstrated by combination of high-speed laser scanning, which would result in single femtosecond laser pulse ablation on surface of silicon, and subsequent wet etching. Microscale concave microlenses with tunable dimensions and accessional aspherical profile are readily obtained on the 1 cm × 1 cm silicon film, which are useful as optical elements for infrared (IR) applications. The aperture diameter and height of the microlens were characterized and the results reveal that they are both proportional to the laser scanning speed. Moreover, the optical property of high-performance silicon MLAs as a reflective homogenizer was investigated for the visible wavelength, and it can be easily extended to IR light.

High-level integration of three-dimensional microcoils array in fused silica.

Rapid and facile creation of three-dimensional (3D) microcoils array in a "lab-on-a-chip" platform is a big challenge in micromachining. Here we report a method based on an improved femtosecond-laser wet-etch (FLWE) technology and metal-microsolidifying process for the fabrication of 3D microcoils array inside fused silica. Based on this approach, we fabricated microcoil arrays such as 3×3 O-shaped microcoils array and 4×4 liner microcoils array. By injecting high-melting-point alloy, the electrocircuit of microcoils array can hardly be disconnected. The microcoils array also exhibits good uniformity and a high integration level. It shows promise as a real application device.

Femtosecond laser controlled wettability of solid surfaces.

Femtosecond laser microfabrication is emerging as a hot tool for controlling the wettability of solid surfaces. This paper introduces four typical aspects of femtosecond laser induced special wettability: superhydrophobicity, underwater superoleophobicity, anisotropic wettability, and smart wettability. The static properties are characterized by the contact angle measurement, while the dynamic features are investigated by the sliding behavior of a liquid droplet. Using different materials and machining methods results in different rough microstructures, patterns, and even chemistry on the solid substrates. So, various beautiful wettabilities can be realized because wettability is mainly dependent on the surface topography and chemical composition. The distinctions of the underlying formation mechanism of these wettabilities are also described in detail.

Unraveling the influence of biogenic volatile organic compounds and their constituents on ozone and SOA formation within the Yellow River Basin, China.

Biogenic volatile organic compounds (BVOC) assume a pivotal role during the formation stages of ozone (O3) and secondary organic aerosols (SOA), serving as their primary precursors. We used the latest MEGAN3.1 model, updated vegetation data and emission factors, combined with MODIS data analysis to simulate and estimate the integrated emissions of BVOC from nine provinces in China's Yellow River Basin in 2018. Following an extensive evaluation of the WRF-CMAQ model utilizing diverse parameters, the simulated and observed values had correlation coefficients between them that ranged from 0.94 to 0.99, implying a favorable outcome in terms of simulation efficacy. The findings from the simulation analysis reveal that the combined BVOC emissions from the nine provinces in the Yellow River Basin reached a total of 6.51 Tg in 2018. Among these provinces, Sichuan, Henan, and Shaanxi ranked highest, with emissions of 1.28 Tg, 1.04 Tg, and 0.96 Tg, respectively. BVOC emissions led to concentrations of 36.72 µg/m³ in the daily maximum 8-h ozone and 0.59 µg/m³ in the average SOA in nine provinces of the Yellow River Basin in July. Isoprene contributed the most to the O3 production with 6.31 µg/m3, and monoterpenes contributed the most to SOA production with 0.45 µg/m3. ΔSOA and ΔOzone are mainly distributed in the belts of central Sichuan Province, southern Shaanxi Province, western Henan Province, northern Qinghai Province, central Inner Mongolia, and southern Shanxi Province, and most of these areas are located 50 km around the Yellow River. O3 and SOA in Taiyuan, Xi'an, Chengdu, and Zhengzhou cities are strongly influenced by the generation of BVOCs. This study provides a reliable scientific basis for the prevention and control of air pollution in the Yellow River Basin.

Multifunctional Electrostatic Droplet Manipulation on the Femtosecond Laser-Prepared Slippery Surfaces.

A strategy to manipulate droplets on the lubricated slippery surfaces using tribostatic electricity is proposed. By employing femtosecond laser-induced porous microstructures, we prepared a slippery surface with ultralow adhesion to various liquids. Electrostatic induction causes the charges within the droplet to be redistributed; thus, the droplet on the as-prepared slippery surfaces can be guided by electrostatic force under the electrostatic field, with controllable sliding direction and unlimited transport distance. The combination of electrostatic interaction and slippery surfaces allows us to manipulate droplets with a wide volume range (from 100 nL to 0.5 mL), charged droplets (including electrostatic attraction and repulsion), corrosive droplets, and even organic droplets with ultralow surface tension. In addition, droplets on tilted surfaces, curved surfaces, and inverted slippery surfaces can also be manipulated. Especially, the slippery surfaces can even allow the electrostatic interaction to manipulate alcohol with surface tension as low as 22.3 mN/m and liquid droplets suspended on a downward surface, which is not possible with reported superhydrophobic substrates. The features of slippery surfaces make the electrostatic manipulation successfully applied in versatile droplet manipulation, droplet patterning, chemical microreaction, transport of solid cargo, targeted delivery of chemicals, and liquid sorting.

Durable Janus membrane with on-demand mode switching fabricated by femtosecond laser.

Despite their notable unidirectional water transport capabilities, Janus membranes are commonly challenged by the fragility of their chemical coatings and the clogging of open microchannels. Here, an on-demand mode-switching strategy is presented to consider the Janus functionality and mechanical durability separately and implement them by simply stretching and releasing the membrane. The stretching Janus mode facilitates unidirectional liquid flow through the hydrophilic micropores-microgrooves channels (PG channels) fabricated by femtosecond laser. The releasing protection mode is designed for the in-situ closure of the PG channels upon encountering external abrasion and impact. The protection mode imparts the Janus membrane robustness to reserve water unidirectional penetration under harsh conditions, such as 2000 cycles mechanical abrasion, 10 days exposure in air and other rigorous tests (sandpaper abrasion, finger rubbing, sand impact and tape peeling). The underlying mechanism of gridded grooves in protecting and enhancing water flow is unveiled. The Janus membrane serves as a fog collector to demonstrate its unwavering mechanical durability in harsh real-world conditions. The presented design strategy could open up new possibilities of Janus membrane in a multitude of applications ranging from multiphase separation devices to fog harvesting and wearable health-monitoring patches.

Controllable adhesive superhydrophobic surfaces based on PDMS microwell arrays.

This paper presents a one-step method to fabricate superhydrophobic surfaces with extremely controllable adhesion based on PDMS microwell arrays. The microwell array structures are rapidly produced on PDMS films by a point-by-point femtosecond laser scanning process. The as-prepared superhydrophobic surfaces show water controllable adhesion that ranges from ultrahigh to ultralow by adjusting the extent of overlap of the adjacent microwells, on which the sliding angle can be controlled from 180° (a water droplet can not slide down even when the as-prepared surface is turned upside down) to 3°. A "micro-airbag effect" is introduced to explain the adhesion transition phenomenon of the microwell array structures. This work provides a facile and promising strategy to fabricate superhydrophobic surfaces with controllable adhesion.

Self-Driving Underwater "Aerofluidics".

Here, the concept of "aerofluidics," in which a system uses microchannels to transport and manipulate trace gases at the microscopic scale to build a highly versatile integrated system based on gas-gas or gas-liquid microinteractions is proposed. A kind of underwater aerofluidic architecture is designed using superhydrophobic surface microgrooves written by a femtosecond laser. In the aqueous medium, a hollow microchannel is formed between the superhydrophobic microgrooves and the water environment, which allows gas to flow freely underwater for aerofluidic devices. Driven by Laplace pressure, gas can be self-transported along various complex patterned paths, curved surfaces, and even across different aerofluidic devices, with an ultralong transportation distance of more than 1 m. The width of the superhydrophobic microchannels of the designed aerofluidic devices is only ≈42.1 µm, enabling the aerofluidic system to achieve accurate gas transportation and control. With the advantages of flexible self-driving gas transportation and ultralong transportation distance, the underwater aerofluidic devices can realize a series of gas control functions, such as gas merging, gas aggregation, gas splitting, gas arrays, gas-gas microreactions, and gas-liquid microreactions. It is believed that underwater aerofluidic technology can have significant applications in gas-involved microanalysis, microdetection, biomedical engineering, sensors, and environmental protection.

Emerging Separation Applications of Surface Superwettability.

Human beings are facing severe global environmental problems and sustainable development problems. Effective separation technology plays an essential role in solving these challenges. In the past decades, superwettability (e.g., superhydrophobicity and underwater superoleophobicity) has succeeded in achieving oil/water separation. The mixture of oil and water is just the tip of the iceberg of the mixtures that need to be separated, so the wettability-based separation strategy should be extended to treat other kinds of liquid/liquid or liquid/gas mixtures. This review aims at generalizing the approach of the well-developed oil/water separation to separate various multiphase mixtures based on the surface superwettability. Superhydrophobic and even superoleophobic surface microstructures have liquid-repellent properties, making different liquids keep away from them. Inspired by the process of oil/water separation, liquid polymers can be separated from water by using underwater superpolymphobic materials. Meanwhile, the underwater superaerophobic and superaerophilic porous materials are successfully used to collect or remove gas bubbles in a liquid, thus achieving liquid/gas separation. We believe that the diversified wettability-based separation methods can be potentially applied in industrial manufacture, energy use, environmental protection, agricultural production, and so on.