Deep-subwavelength single grooves prepared by femtosecond laser direct writing on Si

It is well known that femtosecond laser pulses can easily spontaneously induce deep-subwavelength periodic surface structures on transparent dielectrics but not on non-transparent semiconductors.Nevertheless,in this study,we demonstrate that using high-numerical-aperture 800 nm femtosecond laser direct writing with controlled pulse energy and scanning speed in the near-damage-threshold regime,polarization-dependent deep-subwavelength single grooves with linewidths of~180 nm can be controllably prepared on Si.Generally,the single-groove linewidth increases slightly with increase in the pulse energy and decrease in the scanning speed,whereas the single-groove depth significantly increases from~300 nm to~600 nm with decrease in the scanning speed,or even to over 1μm with multi-processing,indicating the characteristics of transverse clamping and longitudinal growth of such deep-subwavelength single grooves.Energy dispersive spectroscopy composition analysis of the near-groove region confirms that single-groove formation tends to be an ultrafast,non-thermal ablation process,and the oxidized deposits near the grooves are easy to clean up.Furthermore,the results,showing both the strong dependence of groove orientation on laser polarization and the occurrence of double-groove structures due to the interference of pre-formed orthogonal grooves,indicate that the extraordinary field enhancement of strong polarization sensitivity in the deep-subwavelength groove plays an important role in single-groove growth with high stability and collimation.

Laser direct writing of Ga_(2)O_(3)/liquid metal-based flexible humidity sensors

Flexible and wearable humidity sensors play a vital role in daily point-of-care diagnosis and noncontact human-machine interactions.However,achieving a facile and high-speed fabrication approach to realizing flexible humidity sensors remains a challenge.In this work,a wearable capacitive-type Ga_(2)O_(3)/liquid metal-based humidity sensor is demonstrated by a one-step laser direct writing technique.Owing to the photothermal effect of laser,the Ga_(2)O_(3)-wrapped liquid metal particles can be selectively sintered and converted from insulative to conductive traces with a resistivity of 0.19Ω·cm,while the untreated regions serve as active sensing layers in response to moisture changes.Under 95%relative humidity,the humidity sensor displays a highly stable performance along with rapid response and recover time.Utilizing these superior properties,the Ga_(2)O_(3)/liquid metal-based humidity sensor is able to monitor human respiration rate,as well as skin moisture of the palm under different physiological states for healthcare monitoring.

Femtosecond laser direct writing of functional stimulus-responsive structures and applications

Diverse natural organisms possess stimulus-responsive structures to adapt to the surrounding environment.Inspired by nature,researchers have developed various smart stimulus-responsive structures with adjustable properties and functions to address the demands of ever-changing application environments that are becoming more intricate.Among many fabrication methods for stimulus-responsive structures,femtosecond laser direct writing(FsLDW)has received increasing attention because of its high precision,simplicity,true three-dimensional machining ability,and wide applicability to almost all materials.This paper systematically outlines state-of-the-art research on stimulus-responsive structures prepared by FsLDW.Based on the introduction of femtosecond laser-matter interaction and mainstream FsLDW-based manufacturing strategies,different stimulating factors that can trigger structural responses of prepared intelligent structures,such as magnetic field,light,temperature,pH,and humidity,are emphatically summarized.Various applications of functional structures with stimuli-responsive dynamic behaviors fabricated by FsLDW,as well as the present obstacles and forthcoming development opportunities,are discussed.

Direct ink writing to fabricate porous acetabular cups from titanium alloy

Acetabular cups,which are among themost important implants in total hip arthroplasty,are usually made from titanium alloys with high porosity and adequate mechanical properties.The current three-dimensional(3D)printing approaches to fabricate customized acetabular cups have some inherent disadvantages such as high cost and energy consumption,residual thermal stress,and relatively low efficiency.Thus,in this work,a direct ink writing method was developed to print a cup structure at room temperature,followed by multi-step heat treatment to form microscale porous structure within the acetabular cup.Our method is facilitated by the development of a self-supporting titanium-6 aluminum-4 vanadium(Ti64)ink that is composed of Ti64 particles,bentonite yield-stress additive,ultraviolet curable polymer,and photo-initiator.The effects of Ti64 and bentonite concentrations on the rheological properties and printability of inks were systematically investigated.Moreover,the printing conditions,geometrical limitations,and maximum curing depth were explored.Finally,some complex 3D structures,including lattices with different gap distances,honeycomb with a well-defined shape,and an acetabular cup with uniformly distributed micropores,were successfully printed/fabricated to validate the effectiveness of the proposed method.

Periodic transparent nanowires in ITO film fabricated via femtosecond laser direct writing

This paper reports the fabrication of regular large-area laser-induced periodic surface structures(LIPSSs)in indium tin oxide(ITO)films via femtosecond laser direct writing focused by a cylindrical lens.The regular LIPSSs exhibited good properties as nanowires,with a resistivity almost equal to that of the initial ITO film.By changing the laser fluence,the nanowire resistances could be tuned from 15 to 73 kΩ/mm with a consistency of±10%.Furthermore,the average transmittance of the ITO films with regular LIPSSs in the range of 1200-2000 nm was improved from 21%to 60%.The regular LIPSS is promising for transparent electrodes of nano-optoelectronic devices-particularly in the near-infrared band.

A systematic printability study of direct ink writing towards high-resolution rapid manufacturing

Direct ink writing(DIW)holds enormous potential in fabricating multiscale and multi-functional architectures by virtue of its wide range of printable materials,simple operation,and ease of rapid prototyping.Although it is well known that ink rheology and processing parameters have a direct impact on the resolution and shape of the printed objects,the underlying mechanisms of these key factors on the printability and quality of DIW technique remain poorly understood.To tackle this issue,we systematically analyzed the printability and quality through extrusion mechanism modeling and experimental validating.Hybrid non-Newtonian fluid inks were first prepared,and their rheological properties were measured.Then,finite element analysis of the whole DIW process was conducted to reveal the flow dynamics of these inks.The obtained optimal process parameters(ink rheology,applied pressure,printing speed,etc)were also validated by experiments where high-resolution(<100μm)patterns were fabricated rapidly(>70 mm s^(-1)).Finally,as a process research demonstration,we printed a series of microstructures and circuit systems with hybrid inks and silver inks,showing the suitability of the printable process parameters.This study provides a strong quantitative illustration of the use of DIW for the high-speed preparation of high-resolution,high-precision samples.

Memristive feature and mechanism induced by laser-doping in defect-free 2D semiconductor materials

Memristors as non-volatile memory devices have gained numerous attentions owing to their advantages in storage,in-memory computing, synaptic applications, etc. In recent years, two-dimensional(2D) materials with moderate defects have been discovered to exist memristive feature. However, it is very difficult to obtain moderate defect degree in 2D materials, and studied on modulation means and mechanism becomes urgent and essential. In this work, we realized memristive feature with a bipolar switching and a configurable on/off ratio in a two-terminal MoS_(2) device(on/off ratio ~100), for the first time, from absent to present using laser-modulation to few-layer defect-free MoS_(2)(about 10 layers), and its retention time in both high resistance state and low resistance state can reach 2×10^(4) s. The mechanism of the laser-induced memristive feature has been cleared by dynamic Monte Carlo simulations and first-principles calculations. Furthermore, we verified the universality of the laser-modulation by investigating other 2D materials of TMDs. Our work will open a route to modulate and optimize the performance of 2D semiconductor memristive devices.

Preparation and combustion properties of laminated sticks of B-CuO and B-Bi_(2)O_(3)

To explore the composite process of B-CuO and B-Bi_(2)O_(3) two-component laminated sticks,obtain the corresponding sticks with good printing effect,and explore the energy release behavior.In this study,boron,copper oxide,and bismuth trioxide powders were dispersed in the dispersed phase (DMF) using F_(2602) as a binder,and the construction of two-component B-CuO,B-Bi_(2)O_(3),three-component microcomposite,and three-component macro-composite sticks were realized with the help of double nozzle direct ink writing (DIW) technique respectively.The resulting sticks were ignited by a nichrome wire energized with a direct current,and a high-speed camera system was used to record the combustion behavior of the sticks,mark the flame position,and calculate the rate of ignition.The results showed that the B-CuO stick burning rate (42.11 mm·s^(-1)) was much higher than that of B-Bi_(2)O_(3)(17.84 mm·s^(-1)).The formulation with the highest CuO content (ω_(CuO)=58.7%) in the microscale composite of the sticks also had the fastest burning rate of 60.59 mm·s^(-1),as the CuO content decreased (ω_(CuO)=43.5%,29.3%),its burning rate decreased to 34.78 mm·s^(-1),37.97 mm·s^(-1).The stick with the highest copper oxide content(ω_(CuO)=60%) also possessed the highest burning rate (48.84 mm·s^(-1)) in the macro-composite sticks,and the burning rates of the macro-composite sticks with component spacing of 0.1 mm,0.2 mm,and 0.5 mm were 43.34 mm·s^(-1),48.84 mm·s^(-1),and 40.76 mm·s^(-1).

High-rate metal-free MXene microsupercapacitors on paper substrates

MXene is a promising energy storage material for miniaturized microbatteries and microsupercapacitors(MSCs).Despite its superior electrochemical performance,only a few studies have reported MXene-based ultrahigh-rate(>1000 mV s^(−1))on-paper MSCs,mainly due to the reduced electrical conductance of MXene films deposited on paper.Herein,ultrahigh-rate metal-free on-paper MSCs based on heterogeneous MXene/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS)-stack electrodes are fabricated through the combination of direct ink writing and femtosecond laser scribing.With a footprint area of only 20 mm^(2),the on-paper MSCs exhibit excellent high-rate capacitive behavior with an areal capacitance of 5.7 mF cm^(−2)and long cycle life(>95%capacitance retention after 10,000 cycles)at a high scan rate of 1000 mV s^(−1),outperforming most of the present on-paper MSCs.Furthermore,the heterogeneous MXene/PEDOT:PSS electrodes can interconnect individual MSCs into metal-free on-paper MSC arrays,which can also be simultaneously charged/discharged at 1000 mV s^(−1),showing scalable capacitive performance.The heterogeneous MXene/PEDOT:PSS stacks are a promising electrode structure for on-paper MSCs to serve as ultrafast miniaturized energy storage components for emerging paper electronics.

Direct Ink Writing of Highly Conductive MXene Frames for Tunable Electromagnetic Interference Shielding and Electromagnetic Wave-Induced Thermochromism

The highly integrated and miniaturized next-generation electronic products call for high-performance electromagnetic interference(EMI)shielding materials to assure the normal operation of their closely assembled components.However,the most current techniques are not adequate for the fabrication of shielding materials with programmable structure and controllable shielding efficiency.Herein,we demonstrate the direct ink writing of robust and highly conductive Ti3C2Tx MXene frames with customizable structures by using MXene/AlOOH inks for tunable EMI shielding and electromagnetic wave-induced thermochromism applications.The as-printed frames are reinforced by immersing in AlCl_(3)/HCl solution to remove the electrically insulating AlOOH nanoparticles,as well as cross-link the MXene sheets and fuse the filament interfaces with aluminum ions.After freeze-drying,the resultant robust and porous MXene frames exhibit tunable EMI shielding efficiencies in the range of 25-80 dB with the highest electrical conductivity of 5323 S m−1.Furthermore,an electromagnetic wave-induced thermochromic MXene pattern is assembled by coating and curing with thermochromic polydimethylsiloxane on a printed MXene pattern,and its color can be changed from blue to red under the high-intensity electromagnetic irradiation.This work demonstrates a direct ink printing of customizable EMI frames and patterns for tuning EMI shielding efficiency and visualizing electromagnetic waves.

3D direct writing and micro detonation of CL-20 based explosive ink containing O/W emulsion binder

The booming development of DIW technology present an unprecedented prospect in energetic materials field and has attracted great interest due to its relative simplicity and high flexibility of manufacturing.Herein,a novel CL-20 based explosive ink formulation have been developed successfully for MEMS initiation systems via DIW technology.We designed PVA/GAP into an oil-in-water(O/W)emulsion,in the way that the aqueous solution of PVA as water phase,the ethyl acetate solution of GAP as oil phase,the combination of Tween 80 and SDS as emulsifier,BPS as a curing agent of GAP.The ideal formulation with good shear-thinning rheology properties and clear gel point was prepared using only 10 wt%emulsion.The dual-cured network formed during the curing process made the printed sample have good mechanical properties.The printed samples had satisfactory molding effect without cracks or fractures,the crystal form of CL-20 not changed and the thermal stability have improved.Deposition of explosive inks via DIW in micro-scale grooves had excellent detonation performances,which critical detonation size was 1×0.045 mm,detonation velocity was 7129 m/s and when the corner reaching 150°can still detonated stably.This study may open new avenues for developing binder systems in explosive ink formulations.

Direct ink writing of 3D-Honeycombed CL-20 structures with low critical size

3D-Honeycombed CL-20 structures with low critical size of detonation have been fabricated successfully for intelligent weapon systems using a micro-flow direct ink writing(DIW) technology.The CL-20-based explosive ink for DIW technology was prepared by a two-component adhesive system with waterborne polyurethane(WPU) and ethyl cellulose(EC).Not only the preparation of the explosive ink but also the principle of DIW process have been investigated systematically.The explosive ink displayed stro ng shea rthinning behavior that permitted layer-by-laye r deposition from a fine nozzle onto a substrate to produce complex shapes.The EC content was varied to alter the pore structure distribution and rheological behavior of ink samples after curing.The deposited explosive composite materials are of a honeycombed structure with high porosity,and the pore size distribution increases with the increase of EC content.No phase change was observed during the preparation process.Both WPU and EC show good compatibility with CL-20 particles.Apparently high activation energy was realized in the CL-20-based composite ink compared with that of the refined CL-20 due to the presence of non-energetic but stable WPU.The detonation performance of the composite materials can be precisely controlled by an adjustment in the content of binders.The 3D honeyco mbed CL-20 structures,which are fabricated by DIW technology,have a very small critical detonation size of less than 69 μm,as demonstrated by wedge shaped charge test.The ink can be used to create 3D structures with complex geometries not possible with traditional manufacturing techniques,which presents a bright future for the development of intelligent weapon systems.

Femtosecond-laser direct writing 3D micro/nano-lithography using VIS-light oscillator

Here we report a femtosecond laser direct writing(a precise 3D printing also known as two-photon polymerization lithography) of hybrid organic-inorganic SZ2080^(TM)pre-polymer without using any photo-initiator and applying ~100 fs oscillator operating at 517 nm wavelength and 76 MHz repetition rate. The proof of concept was experimentally demonstrated and benchmarking 3D woodpile nanostructures, micro-scaffolds, free-form micro-object “Benchy” and bulk micro-cubes are successfully produced. The essential novelty underlies the fact that non-amplified laser systems delivering just 40-500 p J individual pulses are sufficient for inducing localized cross-linking reactions within hundreds of nanometers in cross sections. And it is opposed to the prejudice that higher pulse energies and lower repetition rates of amplified lasers are necessary for structuring non-photosensitized polymers. The experimental work is of high importance for fundamental understanding of laser enabled nanoscale 3D additive manufacturing and widens technology’ s field of applications where the avoidance of photo-initiator is preferable or is even a necessity, such as micro-optics, nano-photonics, and biomedicine.

Laser direct writing derived robust carbon nitride films with efficient photon-to-electron conversion for multifunctional photoelectrical applications

Carbon nitride,an emerging polymeric semiconductor,has attracted attention in research ranging from photocatalysis to photodetection due to its favorable visible light response and high physicochemical stability.For its practical device application,the fabrication of high-quality carbon nitride films on substrates is essential.However,conventional methodologies to achieve high polymerization of carbon nitride are often accompanied by its decomposition,significantly compromising the film quality.Herein,we report an ultrafast fabrication of carbon nitride film by laser direct writing(LDW).The instantaneous high temperature and pressure during LDW can efficiently boost the polymerization of carbon nitride and suppress its decomposition,resulting in high-quality carbon nitride film with excellent mechanical stability with the substrate.Due to the efficient photon-to-electron conversion,it exhibits an outstanding photoelectrochemical water splitting and optoelectronic detection capability,even under strong acid/alkaline conditions.This study thus offers a facile and efficient LDW strategy for the rapid fabrication of carbon nitride film photoelectrodes,demonstrating its great feasibility in multifunctional photoelectrical applications,including but not limited to photoelectrochemical water splitting and optoelectronic detection.

Bioinspired micro/nanostructured surfaces prepared by femtosecond laser direct writing for multi-functional applications

manufacturing of biomimetic micro/nanostructures due to its specific advantages including high precision,simplicity,and compatibility for diverse materials in comparison with other methods(e.g.ion etching,sol-gel process,chemical vapor deposition,template method,and self-assembly).These biomimetic micro/nanostructured surfaces are of significant interest for academic and industrial research due to their wide range of potential applications,including self-cleaning surfaces,oil-water separation,and fog collection.This review presents the inherent relationship between natural organisms,fabrication methods,micro/nanostructures and their potential applications.Thereafter,we throw a list of current fabrication strategies so as to highlight the advantages of FLDW in manufacturing bioinspired microstructured surfaces.Subsequently,we summarize a variety of typical bioinspired designs(e.g.lotus leaf,pitcher plant,rice leaf,butterfly wings,etc)for diverse multifunctional micro/nanostructures through extreme femtosecond laser processing technology.Based on the principle of interfacial chemistry and geometrical optics,we discuss the potential applications of these functional micro/nanostructures and assess the underlying challenges and opportunities in the extreme fabrication of bioinspired micro/nanostructures by FLDW.This review concludes with a follow up and an outlook of femtosecond laser processing in biomimetic domains.

Reshapeable,rehealable and recyclable sensor fabricated by direct ink writing of conductive composites based on covalent adaptable network polymers

Covalent adaptable network(CAN)polymers doped with conductive nanoparticles are an ideal candidate to create reshapeable,rehealable,and fully recyclable electronics.On the other hand,3D printing as a deterministic manufacturing method has a significant potential to fabricate electronics with low cost and high design freedom.In this paper,we incorporate a conductive composite consisting of polyimine CAN and multi-wall carbon nanotubes into direct-ink-writing 3D printing to create polymeric sensors with outstanding reshaping,repairing,and recycling capabilities.The developed printable ink exhibits good printability,conductivity,and recyclability.The conductivity of printed polyimine composites is investigated at different temperatures and deformation strain levels.Their shape-reforming and Joule heating-induced interfacial welding effects are demonstrated and characterized.Finally,a temperature sensor is 3D printed with defined patterns of conductive pathways,which can be easily mounted onto 3D surfaces,repaired after damage,and recycled using solvents.The sensing capability of printed sensors is maintained after the repairing and recycling.Overall,the 3D printed reshapeable,rehealable,and recyclable sensors possess complex geometry and extend service life,which assist in the development of polymer-based electronics toward broad and sustainable applications.

Self-limiting laser crystallization and direct writing of 2D materials

Direct growth and patterning of atomically thin two-dimensional(2D)materials on various substrates are essential steps towards enabling their potential for use in the next generation of electronic and optoelectronic devices.The conventional gas-phase growth techniques,however,are not compatible with direct patterning processes.Similarly,the condensed-phase methods,based on metal oxide deposition and chalcogenization processes,require lengthy processing times and high temperatures.Here,a novel self-limiting laser crystallization process for direct crystallization and patterning of 2D materials is demonstrated.It takes advantage of significant differences between the optical properties of the amorphous and crystalline phases.Pulsed laser deposition is used to deposit a thin layer of stoichiometric amorphous molybdenum disulfide(MoS2)film(∼3 nm)onto the fused silica substrates.A tunable nanosecond infrared(IR)laser(1064 nm)is then employed to couple a precise amount of power and number of pulses into the amorphous materials for controlled crystallization and direct writing processes.The IR laser interaction with the amorphous layer results in fast heating,crystallization,and/or evaporation of the materials within a narrow processing window.However,reduction of the midgap and defect states in the as crystallized layers decreases the laser coupling efficiency leading to higher tolerance to process parameters.The deliberate design of such laser 2D material interactions allows the selflimiting crystallization phenomena to occur with increased quality and a much broader processing window.This unique laser processing approach allows high-quality crystallization,direct writing,patterning,and the integration of various 2D materials into future functional devices.

Laser Direct Writing of Ag Films from Solution on Si Substrate

Pulsed Nd:YAG laser was used to irradiate Si substrate immersed in AgNO3 ethylene glycol solution to deposit Ag films along the lines scanned by laser on the substrate, which is a photo-thermal decomposing process. The decomposed Ag atoms congregate and form polycrystalline Ag particles. The Ag concentration changes greatly with the total laser energyA absorbed by substrate. Transmission electron microscopy (TEM) observation shows the Ag particles are inlaid in the Si substrate. Auger electron spectrum (AES) shows that the Ag concentration decreases with the increase of the sputtering depth, and there is no oxygen element on the surface of the deposited Ag films.

Angular Dependence of the Second Harmonic Generation Induced by Femtosecond Laser Irradiation in Silica-Based Glasses:Variation with Writing Speed and Pulse Energy

To control second harmonic generation (SHG) in silica-based glasses is crucial for fabricating photonic devices, such as frequency doubling waveguides. Here, we investigated SHG of laser induced nonlinear optical crystals in silica-based glasses, according to writing speed and pulse energy. We observed two regions with different probing laser polarization angular dependence: a) a well-defined cosine-like curve with period of 180° at low pulse energy (0.8 μJ) whatever the writing speed or at high pulse energy (1.4 μJ) with high writing speed (25 μm/s). This is accounted for by a well-defined texture for the nano crystals with their polar axis oriented perpendicular to the writing laser polarization;and b) a double cosine-like curve revealing a second texture of the crystals at high pulse energy (1.4 μJ) with low writing speed (5 μm/s) and with the polar axis oriented closer parallel to the writing laser polarization. Therefore, a SHG dependence on probing laser polarization angle may show high contrast by a correct choice of the writing speed and pulse energy. These results pave the way for elaboration of nonlinear optical devices.

A direct laser-synthesized magnetic metamaterial for low-frequency wideband passive microwave absorption

Microwave absorption in radar stealth technology is faced with challenges in terms of its effectiveness in low-frequency regions.Herein,we report a new laser-based method for producing an ultrawideband metamaterial-based microwave absorber with a highly uniform sheet resistance and negative magnetic permeability at resonant frequencies,which results in a wide bandwidth in the L-to S-band.Control of the electrical sheet resistance uniformity has been achieved with less than 5%deviation at 400Ωsq^(-1)and 6%deviation at 120Ωsq^(-1),resulting in a microwave absorption coefficient between 97.2%and 97.7%within a1.56–18.3 GHz bandwidth for incident angles of 0°–40°,and there is no need for providing energy or an electrical power source during the operation.Porous N-and S-doped turbostratic graphene 2D patterns with embedded magnetic nanoparticles were produced simultaneously on a polyethylene terephthalate substrate via laser direct writing.The proposed low-frequency,wideband,wide-incident-angle,and high-electromagnetic-absorption microwave absorber can potentially be used in aviation,electromagnetic interference(EMI)suppression,and 5G applications.