Recognitions of colored fabrics/laser-patterned metals based on photothermoelectric effects.

Color is the mapping of electromagnetic waves of different wavelengths in human vision. The electronic color recognition system currently in use is mainly based on the photoelectric effect. Here, we demonstrate a color materials' recognition system based on photothermoelectric effects. The system uses a microfabricated thermoelectric generator (TEG) as a platform, which is covered with dye-colored fabric pieces or structure-colored laser-patterned metal sheets. Under light irradiation, the fabrics/metals selectively absorb light and convert it into heat, which flows through the underlying TEG arrays and then converted into electrical signal output to realize the distinction of color and materials. This previously unidentified high-sensitivity TEG detection method provides a potential approach for precise color materials' detection over wide areas and may help understand the mechanism of bionic color recognition.

Hierarchical WO3-x Ultrabroadband Absorbers and Photothermal Converters Grown from Femtosecond Laser-Induced Periodic Surface Structures.

Oxygen-vacancy-rich WO3-x absorbers are gaining increasing attention because of their extensive absorbance-based applications in near-infrared shielding, photocatalysis, sterilization, interfacial evaporator and electrochromic, photochromic, and photothermal fields. Thermal treatment in an oxygen-deficient atmosphere enables us to prepare WO3-x but lacks the capacity for finely manipulating the grown structures. In this work, we present that laser-induced periodic surface structure (LIPSS) obtained by femtosecond laser ablation is a good template to grow various hierarchical WO3-x ultrabroadband absorbers and photothermal converters by thermal oxidation annealing in air. Increasing annealing temperature from 600 to 1000 °C allows the manipulation of WO3-x crystal sizes from ∼70 nm to ∼4 µm, accompanied by a color transition from brown to dark blue and finally to yellow. Benefiting from annealing-induced surface cracks and phase transition into WO3-x (containing both WO3 and W18O49) at 600 °C, excellent UV-vis-NIR-MIR ultrabroadband absorbers were produced: >90% UV-NIR absorbance (0.3-2.5 µm) and 50-90% MIR absorbance (2.5-16 µm), much better than most W-based metamaterial absorbers. The higher the annealing temperature (1000 > 800 > 600 °C), the better the photothermal performances (sample temperature as the indicator) of annealed interfaces due to the increased oxidation rates and resultant thicker oxide layers (6, 150, and 507 µm), a trend which is more apparent upon the irradiation of high-density (3160 mW/cm2) and ultrabroadband (200-2500 nm) light but much less apparent for shorter-band (200-800, 420-800, 800-2500 nm, etc.) and less-intensity (1694, 1540, 1460 mW/cm2, etc.) light irradiation. This phenomenon indicates that (1) higher-performance ultrabroadband absorbers possess a higher photothermal conversion capacity; (2) thicker-WO3-x oxide layer converters are more effective in preserving photothermal heat; and (3) both the W-LIPSS and metal tungsten substrate can quickly dissipate the photothermal heat to inhibit heat accumulation in the oxide photothermal converters. It is also proved that ablation-induced high-pressure shockwaves can produce deformation layers in the subsurfaces to release annealing-induced stresses, beneficial for the formation of less-cracked non-stoichiometric WO3-x interfaces upon annealing. High-pressure shockwaves are also capable of inducing grain refinement of LIPSS, which facilitates a homogeneous growth of small non-stoichiometric metal-oxide crystals upon annealing. Our results indicate that femtosecond laser ablation is a convenient upstream template-fabrication technique compatible with the thermal oxidation annealing method to develop advanced functional oxygen-vacancy metal-oxide interfaces.

Multiscale Hierarchical Micro/Nanostructures Created by Femtosecond Laser Ablation in Liquids for Polarization-Dependent Broadband Antireflection.

In this work, we present the possibility of producing multiscale hierarchical micro/nanostructures by the femtosecond laser ablation of transition metals (i.e., Ta and W) in water and investigate their polarization-dependent reflectance. The hierarchical micro/nanostructures are composed of microscale-grooved, mountain-like and pit-rich structures decorated with hybrid laser-induced periodic surface structures (LIPSSs). The hybrid LIPSSs consist of low/high and ultrahigh spatial frequency LIPSSs (LSFLs/HSFLs and UHSFLs). LSFLs/HSFLs of 400-600 nm in a period are typically oriented perpendicular to the direction of the laser polarization, while UHSFLs (widths: 10-20 nm and periods: 30-50 nm) are oriented perpendicular to the curvatures of LSFLs/HSFLs. On the microstructures with height gradients, the orientations of LSFLs/HSFLs are misaligned by 18°. On the ablated W metasurface, two kinds of UHSFLs are observed. UHSFLs become parallel nanowires in the deep troughs of LSFLs/HSFLs but result in being very chaotic in shallow LSFLs, turning into polygonal nanonetworks. In contrast, chaotic USFLs are not found on the ablated Ta metasurfaces. With the help of Fourier transform infrared spectroscopy, it is found that microgrooves show an obvious polarization-dependent reflectance at wavelengths of 15 and 17.5 µm associated with the direction of the groove, and the integration of microstructures with LSFs/HSFLs/UHSFLs is thus beneficial for enhancing the light absorbance and light trapping in the near-to-mid-infrared (NIR-MIR) range.

Laser-synthesized graphite carbon encased gold nanoparticles with specific reaction channels for efficient oxygen reduction.

Developing novel electrocatalysts with desirable activity and stability is always full of challenge in electrochemical energy conversion. Here, specific carbon shell encapsulated Au (Au@C) nanoparticles are prepared by a laser ablation in liquids method and used as the oxygen reduction reaction (ORR) electrocatalysts. Such Au@C nanoparticles exhibit excellent catalytic activity toward ORR with an onset potential of 0.98 V and a half-wave potential of 0.87 V, better than that of commercial Pt/C. More importantly, the Au@C catalyst exhibits unrivalled stability for 3000 CV cycles for ORR in 0.1 M KOH, dramatically superior to Pt/C and pure Au catalysts. The density functional theory (DFT) calculations and SCN- ions to poison metal-based active sites are conducted to Au@C catalyst, and the results indicate that the structural defects of carbon shells supply an access for the reactants to contact the core Au nanoparticles, causing the catalytic reaction, meanwhile the carbon shells prevent the degeneration of core Au nanoparticles in the harsh electrolytes enhancing the durability of Au effectively.

Magnetic Fe@FeOx, Fe@C and α-Fe2O3 Single-Crystal Nanoblends Synthesized by Femtosecond Laser Ablation of Fe in Acetone.

There are few reports on zero-field-cooled (ZFC) magnetization measurements for Fe@FeOx or FeOx particles synthesized by laser ablation in liquids (LAL) of Fe, and the minimum blocking temperature (TB) of 120 K reported so far is still much higher than those of their counterparts synthesized by chemical methods. In this work, the minimum blocking temperature was lowered to 52 K for 4⁻5 nm α-Fe2O3 particles synthesized by femtosecond laser ablation of Fe in acetone. The effective magnetic anisotropy energy density (Keff) is calculated to be 2.7⁻5.4 × 105 J/m³, further extending the Keff values for smaller hematite particles synthesized by different methods. Large amorphous-Fe@α-Fe2O3 and amorphous-Fe@C particles of 10⁻100 nm in diameter display a soft magnetic behavior with saturation magnetization (Ms) and coercivities (Hc) values of 72.5 emu/g and 160 Oe at 5 K and 61.9 emu/g and 70 Oe at 300 K, respectively, which mainly stem from the magnetism of amorphous Fe cores. Generally, the nanoparticles obtained by LAL are either amorphous or polycrystalline, seldom in a single-crystalline state. This work also demonstrates the possibility of synthesizing single-crystalline α-Fe2O3 hematite crystals of several nanometers with (104), (113), (116) or (214) crystallographic orientations, which were produced simultaneously with other products including carbon encapsulated amorphous Fe (a-Fe@C) and Fe@FeOx core-shell particles by LAL in one step. Finally, the formation mechanisms for these nanomaterials are proposed and the key factors in series events of LAL are discussed.

Spontaneous Shape Alteration and Size Separation of Surfactant-Free Silver Particles Synthesized by Laser Ablation in Acetone during Long-Period Storage.

The technique of laser ablation in liquids (LAL) has already demonstrated its flexibility and capability for the synthesis of a large variety of surfactant-free nanomaterials with a high purity. However, high purity can cause trouble for nanomaterial synthesis, because active high-purity particles can spontaneously grow into different nanocrystals, which makes it difficult to accurately tailor the size and shape of the synthesized nanomaterials. Therefore, a series of questions arise with regards to whether particle growth occurs during colloid storage, how large the particle size increases to, and into which shape the particles evolve. To obtain answers to these questions, here, Ag particles that are synthesized by femtosecond (fs) laser ablation of Ag in acetone are used as precursors to witness the spontaneous growth behavior of the LAL-generated surfactant-free Ag dots (2⁻10 nm) into different polygonal particles (5⁻50 nm), and the spontaneous size separation phenomenon by the carbon-encapsulation induced precipitation of large particles, after six months of colloid storage. The colloids obtained by LAL at a higher power (600 mW) possess a greater ability and higher efficiency to yield colloids with sizes of <40 nm than the colloids obtained at lower power (300 mW), because of the generation of a larger amount of carbon 'captors' by the decomposition of acetone and the stronger particle fragmentation. Both the size increase and the shape alteration lead to a redshift of the surface plasmon resonance (SPR) band of the Ag colloid from 404 nm to 414 nm, after storage. The Fourier transform infrared spectroscopy (FTIR) analysis shows that the Ag particles are conjugated with COO⁻ and OH⁻ groups, both of which may lead to the growth of polygonal particles. The CO and CO2 molecules are adsorbed on the particle surfaces to form Ag(CO)x and Ag(CO2)x complexes. Complementary nanosecond LAL experiments confirmed that the particle growth was inherent to LAL in acetone, and independent of pulse duration, although some differences in the final particle sizes were observed. The nanosecond-LAL yields monomodal colloids, whereas the size-separated, initially bimodal colloids from the fs-LAL provide a higher fraction of very small particles that are <5 nm. The spontaneous growth of the LAL-generated metallic particles presented in this work should arouse the special attention of academia, especially regarding the detailed discussion on how long the colloids can be preserved for particle characterization and applications, without causing a mismatch between the colloid properties and their performance. The spontaneous size separation phenomenon may help researchers to realize a more reproducible synthesis for small metallic colloids, without concern for the generation of large particles.

Two Birds with One Stone: Spontaneous Size Separation and Growth Inhibition of Femtosecond Laser-Generated Surfactant-Free Metallic Nanoparticles via ex Situ SU-8 Functionalization.

Laser ablation in liquids (LAL) offers a facile technique to develop a large variety of surfactant-free nanomaterials with high purity. However, due to the difficulty in the control of the particle synthesis process, the as-prepared nanomaterials always have a broad size distribution with a large polydispersity (σ). Surfactant-free properties can also cause problems with particle growth, which further increases the difficulty in size control of the colloids. Therefore, searching for strategies to simultaneously unify the sizes of colloids and inhibit particle growth has become significantly important for LAL-synthesized nanomaterials to be extensively used for biological, catalytic, and optical applications, in which fields particle size plays an important role. In this work, we present a facile way to simultaneously realize these two goals by ex situ SU-8 photoresist functionalization. Ag nanoparticles (NPs) synthesized by femtosecond laser ablation of silver in acetone at laser powers of 300 and 600 mW were used as starting materials. The synthesized Ag NPs have a broad size distribution between 1 and 200 nm with an average size of ca. 5.9 nm and σ of 127-207%. After ex situ SU-8 functionalization and 6 months storage, most particles larger than 10 nm become aggregates and precipitate, which makes the size distribution narrow with an average diameter of 4-5 nm and σ of 48-78%. The precipitation process is accompanied by the decrease in colloid mass from the initial ∼0.2 to 0.10-0.11 mg after ex situ SU-8 functionalization and 6 months colloid storage. Morphology analysis indicates that ex situ SU-8 functionalization inhibits the particle growth into polygonal nanocrystals. Radical polymerization of SU-8 on Ag NPs is considered to be the reason for both spontaneous size separation and growth inhibition phenomena. Benefiting from Ag NPs embedment and acetone dissolution, the glass-transition temperature of SU-8 photoresist increased from 314 to 331 °C according to thermogravimetric analysis. The universality of ex situ SU-8 functionalization-induced growth inhibition and size separation behaviors is further proved using the Au colloids generated by LAL in acetone. This work is expected to provide a new route for better size control of LAL-synthesized colloids via ex situ photoresist functionalization, although a half of colloidal mass is wasted due to radical polymerization-induced colloidal precipitation.

Laser Synthesis and Processing of Colloids: Fundamentals and Applications.

Driven by functionality and purity demand for applications of inorganic nanoparticle colloids in optics, biology, and energy, their surface chemistry has become a topic of intensive research interest. Consequently, ligand-free colloids are ideal reference materials for evaluating the effects of surface adsorbates from the initial state for application-oriented nanointegration purposes. After two decades of development, laser synthesis and processing of colloids (LSPC) has emerged as a convenient and scalable technique for the synthesis of ligand-free nanomaterials in sealed environments. In addition to the high-purity surface of LSPC-generated nanoparticles, other strengths of LSPC include its high throughput, convenience for preparing alloys or series of doped nanomaterials, and its continuous operation mode, suitable for downstream processing. Unscreened surface charge of LSPC-synthesized colloids is the key to achieving colloidal stability and high affinity to biomolecules as well as support materials, thereby enabling the fabrication of bioconjugates and heterogeneous catalysts. Accurate size control of LSPC-synthesized materials ranging from quantum dots to submicrometer spheres and recent upscaling advancement toward the multiple-gram scale are helpful for extending the applicability of LSPC-synthesized nanomaterials to various fields. By discussing key reports on both the fundamentals and the applications related to laser ablation, fragmentation, and melting in liquids, this Article presents a timely and critical review of this emerging topic.

Germanium Sub-Microspheres Synthesized by Picosecond Pulsed Laser Melting in Liquids: Educt Size Effects.

Pulsed laser melting in liquid (PLML) has emerged as a facile approach to synthesize submicron spheres (SMSs) for various applications. Typically lasers with long pulse durations in the nanosecond regime are used. However, recent findings show that during melting the energy absorbed by the particle will be dissipated promptly after laser-matter interaction following the temperature decrease within tens of nanoseconds and hence limiting the efficiency of longer pulse widths. Here, the feasibility to utilize a picosecond laser to synthesize Ge SMSs (200~1000 nm in diameter) is demonstrated by irradiating polydisperse Ge powders in water and isopropanol. Through analyzing the educt size dependent SMSs formation mechanism, we find that Ge powders (200~1000 nm) are directly transformed into SMSs during PLML via reshaping, while comparatively larger powders (1000~2000 nm) are split into daughter SMSs via liquid droplet bisection. Furthermore, the contribution of powders larger than 2000 nm and smaller than 200 nm to form SMSs is discussed. This work shows that compared to nanosecond lasers, picosecond lasers are also suitable to produce SMSs if the pulse duration is longer than the material electron-phonon coupling period to allow thermal relaxation.

Layered Seed-Growth of AgGe Football-like Microspheres via Precursor-Free Picosecond Laser Synthesis in Water.

Hybrid particles are of great significance in terms of their adjustable optical, electronic, magnetic, thermal and mechanical properties. As a novel technique, laser ablation in liquids (LAL) is famous for its precursor-free, "clean" synthesis of hybrid particles with various materials. Till now, almost all the LAL-generated particles originate from the nucleation-growth mechanism. Seed-growth of particles similar to chemical methods seems difficult to be achieved by LAL. Here, we not only present novel patch-joint football-like AgGe microspheres with a diameter in the range of 1 ~ 7 µm achievable by laser ablation in distilled water but also find direct evidences of their layered seed growth mechanism. Many critical factors contribute to the formation of AgGe microspheres: fast laser-generated plasma process provide an excellent condition for generating large amount of Ge and Ag ions/atoms, their initial nucleation and galvanic replacement reaction, while cavitation bubble confinement plays an important role for the increase of AgGe nuclei and subsequent layered growth in water after bubble collapse. Driven by work function difference, Ge acts as nucleation agent for silver during alloy formation. This new seed-growth mechanism for LAL technique opens new opportunities to develop a large variety of novel hybrid materials with controllable properties.

Rapid fabrication of large-area concave microlens arrays on PDMS by a femtosecond laser.

A fast and single-step process is developed for the fabrication of low-cost, high-quality, and large-area concave microlens arrays (MLAs) by the high-speed line-scanning of femtosecond laser pulses. Each concave microlens can be generated by a single laser pulse, and over 2.78 million microlenses were fabricated on a 2 × 2 cm(2) polydimethylsiloxane (PDMS) sheet within 50 min, which greatly enhances the processing efficiency compared to the classical laser direct writing method. The mechanical pressure induced by the expansion of the laser-induced plasmas as well as a long resolidifing time is the reason for the formation of smooth concave spherical microstructures. We show that uniform microlenses with different diameters and depths can be controlled by adjusting the power of laser pulses. Their high-quality optical performance is also demonstrated in this work.

Bioinspired wetting surface via laser microfabrication.

Bioinspired special wettibilities including superhydrophobicity and tunable adhesive force have drawn considerable attention because of their significant potential for fundamental research and practical applications. This review summarizes recent progress in the development of bioinspired wetting surfaces via laser microfabrication, with a focus on controllable, biomimetic, and switchable wetting surfaces, as well as their applications in biology, microfluidic, and paper-based devices, all of which demonstrate the ability of laser microfabrication in producing various multiscale structures and its adaptation in a great variety of materials. In particular, compared to other techniques, laser microfabrication can realize special modulation ranging from superhydrophilic to superhydrophobic without the assistance of fluorination, allowing much more freedom to achieve complex multiple-wettability integration. The current challenges and future research prospects of this rapidly developing field are also being discussed. These approaches open the intriguing possibility of the development of advanced interfaces equipped with the integration of more functionalities.

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.

A simple way to achieve pattern-dependent tunable adhesion in superhydrophobic surfaces by a femtosecond laser.

In this paper, we present a new approach to the tunable adhesive superhydrophobic surfaces consisting of periodic hydrophobic patterns and superhydrophobic structures by femtosecond (fs) laser irradiation on silicon. The surfaces are composed of periodic hydrophobic patterns (triangle, circle, and rhombus) and superhydrophobic structures (dual-scale spikes induced by a fs laser). Our results reveal that the adhesive forces of as-prepared surfaces can be tuned by varying the area ratio (AR(s-h)) of superhydrophobic domain to hydrophobic domain, thus resulting in tunable static and dynamic wettabilities. By increasing AR(s-h), (i) the static wetting property, which is characterized by the minimum water droplet volume that enables a droplet to land on the surface, can be tailored from 1 µL to 9 µL; (ii) the sliding angle can be flexibly adjusted, ranging from >90° (a droplet cannot slide off when the sample is positioned upside down) to 5°; and (iii) the droplet rebound behaviors can be modulated from partial rebound to triple rebound. In addition, the Cassie-Baxter model and the sliding angle model are used to speculate the contact angles and sliding angles to provide potentially theoretical models to design slippery-to-sticky superhydrophobic surfaces. The tunable adhesive superhydrophobic surfaces achieved by fs laser microfabrication may be potentially used in microfluidic systems to modulate the mobility of liquid droplets.

Anisotropic wetting on microstrips surface fabricated by femtosecond laser.

In this paper, we present a new method to realize anisotropy by restricting a droplet on an unstructured Si hydrophobic domain between two superhydrophobic strips fabricated by femtosecond laser. The water contact angles and corresponding water baseline length were investigated. The results showed that anisotropy would vary with the volume-induced pinning-depinning-repinning behavior of the droplet. Furthermore, through the observation of water response on small Si domain, the adhesive force of the structure is proven to be the key factor giving rise to the anisotropy wetting. This phenomenon could potentially be used as a model for fundamental research, and such structures could be utilized to control large volume in microfluidic devices, lab-on-chip system, microreactors, and self-cleaning surfaces.