3D Printing of Hierarchical Structures Made of Inorganic Silicon-Rich Glass Featuring Self-Forming Nanogratings.

Hierarchical structures are abundant in nature, such as in the superhydrophobic surfaces of lotus leaves and the structural coloration of butterfly wings. They consist of ordered features across multiple size scales, and their advantageous properties have attracted enormous interest in wide-ranging fields including energy storage, nanofluidics, and nanophotonics. Femtosecond lasers, which are capable of inducing various material modifications, have shown promise for manufacturing tailored hierarchical structures. However, existing methods, such as multiphoton lithography and three-dimensional (3D) printing using nanoparticle-filled inks, typically involve polymers and suffer from high process complexity. Here, we demonstrate the 3D printing of hierarchical structures in inorganic silicon-rich glass featuring self-forming nanogratings. This approach takes advantage of our finding that femtosecond laser pulses can induce simultaneous multiphoton cross-linking and self-formation of nanogratings in hydrogen silsesquioxane. The 3D printing process combines the 3D patterning capability of multiphoton lithography and the efficient generation of periodic structures by the self-formation of nanogratings. We 3D-printed micro-supercapacitors with large surface areas and a high areal capacitance of 1 mF/cm2 at an ultrahigh scan rate of 50 V/s, thereby demonstrating the utility of our 3D printing approach for device applications in emerging fields such as energy storage.

Laser Direct Writing of Setaria Virids-Inspired Hierarchical Surface with TiO2 Coating for Anti-Sticking of Soft Tissue.

In minimally invasive surgery, the tendency for human tissue to adhere to the electrosurgical scalpel can complicate procedures and elevate the risk of medical accidents. Consequently, the development of an electrosurgical scalpel with an anti-sticking coating is critically important. Drawing inspiration from nature, we identified that the leaves of Setaria Virids exhibit exceptional non-stick properties. Utilizing this natural surface texture as a model, we designed and fabricated a specialized anti-sticking surface for electrosurgical scalpels. Employing nanosecond laser direct writing ablation technology, we created a micro-nano textured surface on the high-frequency electrosurgical scalpel that mimics the structure found on Setaria Virids leaves. Subsequently, a TiO2 coating was deposited onto the ablated scalpel surface via magnetron sputtering, followed by plasma-induced hydrophobic modification and treatment with octadecyltrichlorosilane (OTS) to enhance the surface's affinity for silicone oil, thereby constructing a self-lubricating and anti-sticking surface. The spreading behavior of deionized water, absolute ethanol, and dimethyl silicone oil on this textured surface is investigated to confirm the effectiveness of the self-lubrication mechanism. Furthermore, the sticking force and quality are compared between the anti-sticking electrosurgical scalpel and a standard high-frequency electrosurgical scalpel to demonstrate the efficacy of the nanosecond laser-ablated micro-nano texture in preventing sticking. The findings indicate that the self-lubricating anti-sticking surface fabricated using this texture exhibits superior anti-sticking properties.

High-Extraction-Rate Ta2O5-Core/SiO2-Clad Photonic Waveguides on Silicon Fabricated by Photolithography-Assisted Chemo-Mechanical Etching (PLACE).

We demonstrate high-extraction-rate Ta2O5-core/SiO2-clad photonic waveguides on silicon fabricated by the photolithography-assisted chemo-mechanical etching technique. Low-confinement waveguides of larger than 70% coupling efficiency with optical fibers and medium propagation loss around 1 dB/cm are investigated in the experiment. Monolithic microring resonators based on Ta2O5 waveguides have shown the quality factors to be above 105 near 1550 nm. The demonstrated Ta2O5 waveguides and their fabrication method hold great promise in various cost-effective applications, such as optical interconnecting and switching.

Laser-induced CdS/TiO2/graphene dual photoanodes for ratiometric self-powered photoelectrochemical sensor: an innovative approach for aflatoxin B1 detection.

A ratiometric self-powered photoelectrochemical sensor based on laser direct writing technology was constructed to address the problem that the conventional single-signal detection mode was susceptible to the influence of instrumentation and environmental factors, which interfered with the detection results. Laser-induced CdS/TiO2/Graphene was prepared as dual photoanodes (PA1 and PA2), which were controlled by multiplexed switches to form a photocatalytic fuel cell with Pt cathode. By modifying the aptamer of aflatoxin B1 (AFB1) on the photoanode surface, the target was specifically captured to the electrode surface to form a biological complex, which increased the steric hindrance and affected the electron transfer, thus reducing the output signal of the sensor. Targets with different concentrations were incubated on the surface of PA1, and targets with fixed concentrations were incubated on the surface of PA2. Under the control of the multiplex switch, the output signals of the two photoanodes were recorded, and the ratio of these two signals was used as the basis for the quantitative detection of AFB1. The sensor output was linearly increasing with the logarithm of AFB1 concentration from 1.0 to 150 ng mL-1 and the detection limit was 0.0974 ng mL-1. Additionally, this method had good stability, fast response, and good selectivity to real samples, providing an effective method for food safety monitoring.

Toward Integrated Multifunctional Laser-Induced Graphene-Based Skin-Like Flexible Sensor Systems.

The burgeoning demands for health care and human-machine interfaces call for the next generation of multifunctional integrated sensor systems with facile fabrication processes and reliable performances. Laser-induced graphene (LIG) with highly tunable physical and chemical characteristics plays vital roles in developing versatile skin-like flexible or stretchable sensor systems. This Progress Report presents an in-depth overview of the latest advances in LIG-based techniques in the applications of flexible sensors. First, the merits of the LIG technique are highlighted especially as the building blocks for flexible sensors, followed by the description of various fabrication methods of LIG and its variants. Then, the focus is moved to diverse LIG-based flexible sensors, including physical sensors, chemical sensors, and electrophysiological sensors. Mechanisms and advantages of LIG in these scenarios are described in detail. Furthermore, various representative paradigms of integrated LIG-based sensor systems are presented to show the capabilities of LIG technique for multipurpose applications. The signal cross-talk issues are discussed with possible strategies. The LIG technology with versatile functionalities coupled with other fabrication strategies will enable high-performance integrated sensor systems for next-generation skin electronics.

Laser Fabrication of Multi-Dimensional Perovskite Patterns with Intelligent Anti-Counterfeiting Applications.

Perovskites have gained widespread attention across various fields such as photovoltaics, displays, and imaging. Despite their promising applications, achieving precise and high-quality patterning of perovskite films remains a challenge. In this study, femtosecond laser direct writing technology is utilized to achieve rapid and highly precise micro/nanofabrication on perovskites. The study successfully fabricates multiple structured and emission-tunable perovskite patterns composed of A2(FA)n-1PbnX3n+1 (A represents a series of long-chain amine cations, and X = Cl, Br, I), encompassing 2D, quasi-2D, and 3D structures. The study delves into the intricate interplay between fabrication technology and the growth of multi-dimensional perovskites: higher repetition rates, coupled with appropriate laser power, prove more conducive to perovskite growth. By employing precise halogen element design, the simultaneous generation of two distinct color quick-response (QR) code patterns is achieved through one-step laser processing. These mirrored QR codes offer a novel approach to anti-counterfeiting. To further enhance anti-counterfeiting capabilities, artificial intelligence (AI)-based methods are introduced for recognizing patterned perovskite anti-counterfeiting labels. The combination of deep learning algorithms and a non-deterministic manufacturing process provides a convenient means of identification and creates unclonable features. This integration of materials science, laser fabrication, and AI offers innovative solutions for the future of security features.

7D High-Dynamic Spin-Multiplexing.

Multiplexing technology creates several orthogonal data channels and dimensions for high-density information encoding and is irreplaceable in large-capacity information storage, and communication, etc. The multiplexing dimensions are constructed by light attributes and spatial dimensions. However, limited by the degree of freedom of interaction between light and material structure parameters, the multiplexing dimension exploitation method is still confused. Herein, a 7D Spin-multiplexing technique is proposed. Spin structures with four independent attributes (color center type, spin axis, spatial distribution, and dipole direction) are constructed as coding basic units. Based on the four independent spin physical effects, the corresponding photoluminescence wavelength, magnetic field, microwave, and polarization are created into four orthogonal multiplexing dimensions. Combined with the 3D of space, a 7D multiplexing method is established, which possesses the highest dimension number compared with 6 dimensions in the previous study. The basic spin unit is prepared by a self-developed laser-induced manufacturing process. The free state information of spin is read out by four physical quantities. Based on the multiple dimensions, the information is highly dynamically multiplexed to enhance information storage efficiency. Moreover, the high-dynamic in situ image encryption/marking is demonstrated. It implies a new paradigm for ultra-high-capacity storage and real-time encryption.

3D Directional Assembly of Liquid Crystal Molecules.

The precise construction of hierarchically long-range ordered structures using molecules as fundamental building blocks can fully harness their anisotropy and potential. However, the 3D, high-precision, and single-step directional assembly of molecules is a long-pending challenge. Here, a 3D directional molecular assembly strategy via femtosecond laser direct writing (FsLDW) is proposed and the feasibility of this approach using liquid crystal (LC) molecules as an illustrative example is demonstrated. The physical mechanism for femtosecond (fs) laser-induced assembly of LC molecules is investigated, and precise 3D arbitrary assembly of LC molecules is achieved by defining the discretized laser scanning pathway. Additionally, an LC-based Fresnel zone plate array with polarization selection and colorization imaging functions is fabricated to further illustrate the potential of this method. This study not only introduces a 3D high-resolution alignment method for LC-based functional devices but also establishes a universal protocol for the precise 3D directional assembly of anisotropic molecules.

Amorphous/Crystalline Phases Mixed Nanosheets Array Rich in Oxygen Vacancies Boost Oxygen Evolution Reaction of Spinel Oxides in Alkaline Media.

As promising oxygen evolution reaction (OER) catalysts, spinel-type oxides face the bottleneck of weak adsorption for oxygen-containing intermediates, so it is challenging to make a further breakthrough in remarkably lowering the OER overpotential. In this study, a novel strategy is proposed to substantially enhance the OER activity of spinel oxides based on amorphous/crystalline phases mixed spinel FeNi2O4 nanosheets array, enriched with oxygen vacancies, in situ grown on a nickel foam (NF). This unique architecture is achieved through a one-step millisecond laser direct writing method. The presence of amorphous phases with abundant oxygen vacancies significantly enhances the adsorption of oxygen-containing intermediates and changes the rate-determining step from OH*→O* to O*→OOH*, which greatly reduces the thermodynamic energy barrier. Moreover, the crystalline phase interweaving with amorphous domains serves as a conductive shortcut to facilitate rapid electron transfer from active sites in the amorphous domain to NF, guaranteeing fast OER kinetics. Such an anodic electrode exhibits a nearly ten fold enhancement in OER intrinsic activity compared to the pristine counterpart. Remarkably, it demonstrates record-low overpotentials of 246 and 315 mV at 50 and 500 mA cm-2 in 1 m KOH with superior long-term stability, outperforming other NiFe-based spinel oxides catalysts.

Femtosecond Laser Direct Writing of Flexible Electronic Devices: A Mini Review.

By virtue of its narrow pulse width and high peak power, the femtosecond pulsed laser can achieve high-precision material modification, material additive or subtractive, and other forms of processing. With additional good material adaptability and process compatibility, femtosecond laser-induced application has achieved significant progress in flexible electronics in recent years. These advancements in the femtosecond laser fabrication of flexible electronic devices are comprehensively summarized here. This review first briefly introduces the physical mechanism and characteristics of the femtosecond laser fabrication of various electronic microdevices. It then focuses on effective methods of improving processing efficiency, resolution, and size. It further highlights the typical progress of applications, including flexible energy storage devices, nanogenerators, flexible sensors, and detectors, etc. Finally, it discusses the development tendency of ultrashort pulse laser processing. This review should facilitate the precision manufacturing of flexible electronics using a femtosecond laser.

Foldable paper-based photoelectrochemical biosensor based on etching reaction of CoOOH nanosheets-coated laser-induced PbS/CdS/graphene for sensitive detection of ampicillin.

Timely and rapid detection of antibiotic residues in the environment is conducive to safeguarding human health and promoting an ecological virtuous cycle. A foldable paper-based photoelectrochemical (PEC) sensor was successfully developed for the detection of ampicillin (AMP) based on glutathione/zirconium dioxide hollow nanorods/aptamer (GSH@ZrO2 HS@apt) modified cellulose paper as a reactive zone with laser direct-writing lead sulfide/cadmium sulfide/graphene (PbS/CdS/LIG) as photoelectrode and cobalt hydroxide (CoOOH) as a photoresist material. Initially, AMP was introduced into the paper-based reaction zone as a biogate aptamer, which specifically recognized the target and then left the ZrO2 HS surface, releasing glutathione (GSH) encapsulated inside. Subsequently, the introduction of GSH into the reaction region and etching of CoOOH nanosheets to expose the PbS/CdS/LIG photosensitive material increased photocurrent. Under optimal conditions, the paper-based PEC biosensor showed a linear response to AMP in the range of 5.0 - 2 × 104 pM with a detection limit of 1.36 pM (S/N = 3). In addition, the constructed PEC sensing platform has excellent selectivity, high stability and favorable reproducibility, and can be used to assess AMP residue levels in various real water samples (milk, tap water, river water), indicating its promising application in environmental antibiotic detection.

Surface-Enhanced Raman Scattering Based on Sb2S3 Microstructures via Femtosecond Laser Direct Writing.

The noble-metal-free surface-enhanced Raman scattering (SERS) substrates have gained significant attention due to their abundant sources, signal uniformity, biocompatibility, and chemical stability. However, the lack of controllable synthesis and fabrication methods for high-SERS-activity noble-metal-free substrates hinders their practical applications. In this study, we demonstrate the use of a femtosecond laser direct writing technique to precisely manipulate and modify microstructures, resulting in enhanced SERS signals from Sb2S3 nonmetal-oxide semiconductor materials. Compared with unpatterned Sb2S3 samples, the Sb2S3 microstructures exhibited up to a 16-fold increase in Raman scattering intensity. Interestingly, our results indicate that the femtosecond laser can induce a transformation in the crystalline state of Sb2S3 and significantly enhance the Raman spectrum signal within the Sb2S3 microstructures. This enhancement is also highly dependent on the period and depth of the microstructures, possibly due to the cavity effects, resulting in a stronger local field enhancement.

Automatically Aligned and Environment-Friendly Twisted Stacking Terahertz Chiral Metasurface with Giant Circular Dichroism for Rapid Biosensing.

Chiral metasurfaces are capable of generating a huge superchiral field, which has great potential in optoelectronics and biosensing. However, the conventional fabrication process suffers greatly from time consumption, high cost, and difficult multilayer alignment, which hinder its commercial application. Herein, we propose a twisted stacking carbon-based terahertz (THz) chiral metasurface (TCM) based on laser-induced graphene (LIG) technology. By repeating a two-step process of sticking a polyimide film, followed by laser direct writing, the two layers of the TCM are aligned automatically in the fabrication. Laser manufacturing also brings such high processing speed that a TCM with a size of 15 × 15 mm can be prepared in 60 s. In addition, due to the greater dissipation of LIG than that of metals in the THz band, a giant circular dichroism (CD) of +99.5 to -99.6% is experimentally realized. The THz biosensing of bovine serum albumin enhanced by the proposed TCMs is then demonstrated. A wide sensing range (0.5-50 mg mL-1) and a good sensitivity [ΔCD: 2.09% (mg mL-1)-1, Δf: 0.0034 THz (mg mL-1)-1] are proved. This LIG-based TCM provides an environment-friendly platform for chiral research and has great application potential in rapid and low-cost commercial biosensing.

Printing 3D Metallic Structures in Porous Matrix.

The fabrication of metallic micro/nanostructures has great potential for advancing optoelectronic microdevices. Over the past decade, femtosecond laser direct writing (FsLDW) technology has played a crucial role in driving progress in this field. In this study, silica gel glass is used as a supporting medium, and FsLDW is employed to reduce gold and palladium ions using 7-Diethylamino-3-thenoylcoumarin (DETC) as a two-photon sensitizer, enabling the printing of conductive multilayered and 3D metallic structures. How the pore size of the silica gel glass affects the electrical conductivity of printed metal wires is systematically examined. This 3D printing method is versatile and offers expanded opportunities for applying metallic micro/nanostructures in optoelectronic devices.

Selective CW Laser Synthesis of MoS2 and Mixture of MoS2 and MoO2 from (NH4)2MoS4 Film.

Very recently, the synthesis of 2D MoS2 and WS2 through pulsed laser-directed thermolysis can achieve wafer-scale and large-area structures, in ambient conditions. In this paper, we report the synthesis of MoS2 and MoS2 oxides from (NH4)2MoS4 film using a visible continuous-wave (CW) laser at 532 nm, instead of the infrared pulsed laser for the laser-directed thermolysis. The (NH4)2MoS4 film is prepared by dissolving its crystal powder in DI water, sonicating the solution, and dip-coating onto a glass slide. We observed a laser intensity threshold for the laser synthesis of MoS2, however, it occurred in a narrow laser intensity range. Above that range, a mixture of MoS2 and MoO2 is formed, which can be used for a memristor device, as demonstrated by other research groups. We did not observe a mixture of MoS2 and MoO3 in the laser thermolysis of (NH4)2MoS4. The laser synthesis of MoS2 in a line pattern is also achieved through laser scanning. Due to of the ease of CW beam steering and the fine control of laser intensities, this study can lead toward the CW laser-directed thermolysis of (NH4)2MoS4 film for the fast, non-vacuum, patternable, and wafer-scale synthesis of 2D MoS2.

Flexible Copper-Based Thermistors Fabricated by Laser Direct Writing for Low-Temperature Sensing.

With the flexibilization tendency of traditional electronics, developing sensing devices for the low-temperature field is demanding. Here, we fabricated a flexible copper-based thermistor by a laser direct writing process with Cu ion precursors. The copper-based thermistor performs with excellent temperature sensing ability and high stability under different environments. We discussed the effect of laser power on the temperature sensitivity of the copper-based thermistor, explained the sensing mechanism of the as-written copper-based films, and fabricated a temperature sensor array for realizing temperature management in a specific zone. All of the investigations have demonstrated that such copper-based thermistors can be used as candidate devices for low-temperature sensing fields.

All laser direct writing process for temperature sensor based on graphene and silver.

A highly sensitive temperature sensing array is prepared by all laser direct writing (LDW) method, using laser induced silver (LIS) as electrodes and laser induced graphene (LIG) as temperature sensing layer. A finite element analysis (FEA) photothermal model incorporating a phase transition mechanism is developed to investigate the relationship between laser parameters and LIG properties, providing guidance for laser processing parameters selection with laser power of 1-5 W and laser scanning speed (greater than 50 mm/s). The deviation of simulation and experimental data for widths and thickness of LIG are less than 5% and 9%, respectively. The electrical properties and temperature responsiveness of LIG are also studied. By changing the laser process parameters, the thickness of the LIG ablation grooves can be in the range of 30-120 µm and the resistivity of LIG can be regulated within the range of 0.031-67.2 Ω·m. The percentage temperature coefficient of resistance (TCR) is calculated as - 0.58%/°C. Furthermore, the FEA photothermal model is studied through experiments and simulations data regarding LIS, and the average deviation between experiment and simulation is less than 5%. The LIS sensing samples have a thickness of about 14 µm, an electrical resistivity of 0.0001-100 Ω·m is insensitive to temperature and pressure stimuli. Moreover, for a LIS-LIG based temperature sensing array, a correction factor is introduced to compensate for the LIG temperature sensing being disturbed by pressure stimuli, the temperature measurement difference is decreased from 11.2 to 2.6 °C, indicating good accuracy for temperature measurement.

Direct in Situ Fabrication of Multicolor Afterglow Carbon Dot Patterns with Transparent and Traceless Features via Laser Direct Writing.

Multicolor afterglow patterns with transparent and traceless features are important for the exploration of new functionalities and applications. Herein, we report a direct in situ patterning technique for fabricating afterglow carbon dots (CDs) based on laser direct writing (LDW) for the first time. We explore a facile step-scanning method that reduces the heat-affected zone and avoids uneven heating, thus producing a fine-resolution afterglow CD pattern with a minimum line width of 80 µm. Unlike previous LDW-induced luminescence patterns, the patterned CD films are traceless and transparent, which is mainly attributed to a uniform heat distribution and gentle temperature rise process. Interestingly, by regulating the laser parameters and CD precursors, an increased carbonization and oxidation degree of CDs could be obtained, thus enabling time-dependent, tunable afterglow colors from blue to red. In addition, we demonstrate their potential applications in the in situ fabrication of flexible and stretchable optoelectronics.

Large Field-of-View Nonlinear Holography in Lithium Niobate.

A nonlinear holographic technique is capable of processing optical information in the newly generated optical frequencies, enabling fascinating functions in laser display, security storage, and image recognition. One popular nonlinear hologram is based on a periodically poled lithium niobate (LN) crystal. However, due to the limitations of traditional fabrication techniques, the pixel size of the LN hologram is typically several micrometers, resulting in a limited field-of-voew (FOV) of several degrees. Here, we experimentally demonstrate an ultra-high-resolution LN hologram by using the laser poling technique. The minimal pixel size reaches 200 nm, and the FOV is extended above 120° in our experiments. The image distortions at large view angles are effectively suppressed through the Fourier transform. The FOV is further improved by combining multiple diffraction orders of SH fields. The ultimate FOV under our configuration is decided by a Fresnel transmission. Our results pave the way for expanding the applications of nonlinear holography to wide-view imaging and display.

A High-Performance Strain Sensor for the Detection of Human Motion and Subtle Strain Based on Liquid Metal Microwire.

Flexible strain sensors have a wide range of applications, such as human motion monitoring, wearable electronic devices, and human-computer interactions, due to their good conformability and sensitive deformation detection. To overcome the internal stress problem of solid sensing materials during deformation and prepare small-sized flexible strain sensors, it is necessary to choose a more suitable sensing material and preparation technology. We report a simple and high-performance flexible strain sensor based on liquid metal nanoparticles (LMNPs) on a polyimide substrate. The LMNPs were assembled using the femtosecond laser direct writing technology to form liquid metal microwires. A wearable strain sensor from the liquid metal microwire was fabricated with an excellent gauge factor of up to 76.18, a good linearity in a wide sensing range, and a fast response/recovery time of 159 ms/120 ms. Due to these extraordinary strain sensing performances, the strain sensor can monitor facial expressions in real time and detect vocal cord vibrations for speech recognition.