Two-dimensional laser-induced periodic surface structures formed on crystalline silicon by GHz burst mode femtosecond laser pulses

Femtosecond laser pulses with GHz burst mode that consist of a series of trains of ultrashort laser pulses with a pulse interval of several hundred picoseconds offer distinct features in material processing that cannot be obtained by the conventional irradiation scheme of femtosecond laser pulses(single-pulse mode).However,most studies using the GHz burst mode femtosecond laser pulses focus on ablation of materials to achieve high-efficiency and high-quality material removal.In this study,we explore the ability of the GHz burst mode femtosecond laser processing to form laser-induced periodic surface structures(LIPSS)on silicon.It is well known that the direction of LIPSS formed by the single-pulse mode with linearly polarized laser pulses is typically perpendicular to the laser polarization direction.In contrast,we find that the GHz burst mode femtosecond laser(wavelength:1030 nm,intra-pulse duration:220 fs,intra-pulse interval time(intra-pulse repetition rate):205 ps(4.88 GHz),burst pulse repetition rate:200 kHz)creates unique two-dimensional(2D)LIPSS.We regard the formation mechanism of 2D LIPSS as the synergetic contribution of the electromagnetic mechanism and the hydrodynamic mechanism.Specifically,generation of hot spots with highly enhanced electric fields by the localized surface plasmon resonance of subsequent pulses in the bursts within the nanogrooves of one-dimensional LIPSS formed by the preceding pulses creates 2D LIPSS.Additionally,hydrodynamic instability including convection flow determines the final structure of 2D LIPSS.

Large-area straight,regular periodic surface structures produced on fused silica by the interference of two femtosecond laser beams through cylindrical lens

Inhomogeneity and low efficiency are two important factors that limit the application of laser-induced periodic surface structures(LIPSSs),especially on glass surfaces.In this study,two-beam interference(TBI)of femtosecond lasers was used to produce large-area straight LIPSSs on fused silica using cylindrical lenses.Compared with those produced us-ing a single circular or cylindrical lens,the LIPSSs produced by TBI are much straighter and more regular.Depending on the laser fluence and scanning velocity,LIPSSs with grating-like or spaced LIPSSs are produced on the fused silica sur-face.Their structural colors are blue,green,and red,and only green and red,respectively.Grating-like LIPSS patterns oriented in different directions are obtained and exhibit bright and vivid colors,indicating potential applications in surface coloring and anti-counterfeiting logos.

Enhancement of photocatalytic activity by femtosecond-laser induced periodic surface structures of Si

Laser induced periodic surface structures(LIPSS)represent a kind of top down approach to produce highly reproducible nano/microstructures without going for any sophisticated process of lithography.This method is much simpler and cost effective.In this work,LIPSS on Si surfaces were generated using femtosecond laser pulses of 800 nm wavelength.Photocatalytic substrates were prepared by depositing TiO2 thin films on top of the structured and unstructured Si wafer.The coatings were produced by sputtering from a Ti target in two different types of oxygen atmospheres.In first case,the oxygen pressure within the sputtering chamber was chosen to be high(3×10^–2 mbar)whereas it was one order of magnitude lower in second case(2.1×10^–3 mbar).In photocatalytic dye decomposition study of Methylene blue dye it was found that in the presence of LIPSS the activity can be enhanced by 2.1 and 3.3 times with high pressure and low pressure grown TiO2 thin films,respectively.The increase in photocatalytic activity is attributed to the enlargement of effective surface area.In comparative study,the dye decomposition rates of TiO2 thin films grown on LIPSS are found to be much higher than the value for standard reference thin film material Pilkington Activ^TM.

Femtosecond laser-induced periodic surface structures on hard and brittle materials

Hard and brittle materials have high hardness,excellent optical stability,chemical stability,and high thermal stability.Hence,they have huge application potential in various fields,such as optical components,substrate materials,and quantum information,especially under harsh conditions,such as high temperatures and high pressures.Femtosecond laser direct writing technology has greatly promoted the development of femtosecond laser-induced periodic surface structure(Fs-LIPSS or LIPSS by a femtosecond laser)applications of hard and brittle materials due to its high precision,controllability,and three-dimensional processing ability.Thus far,LIPSSs have been widely used in material surface treatment,optoelectronic devices,and micromechanics.However,a consensus has not been reached regarding the formation mechanism of LIPSSs on hard and brittle materials.In this paper,three widely accepted LIPSS formation mechanisms are introduced,and the characteristics and applications of LIPSSs on diamonds,silicon,silicon carbide,and fused silica surfaces in recent years are summarized.In addition,the application prospects and challenges of LIPSSs on hard and brittle materials by a femtosecond laser are discussed.

Ultrafast dynamics of femtosecond laser-induced high spatial frequency periodic structures on silicon surfaces

Femtosecond laser-induced periodic surface structures(LIPSS)have been extensively studied over the past few decades.In particular,the period and groove width of high-spatial-frequency LIPSS(HSFL)is much smaller than the diffraction limit,making it a useful method for efficient nanomanufacturing.However,compared with the low-spatial-frequency LIPSS(LSFL),the structure size of the HSFL is smaller,and it is more easily submerged.Therefore,the formation mechanism of HSFL is complex and has always been a research hotspot in this field.In this study,regular LSFL with a period of 760 nm was fabricated in advance on a silicon surface with two-beam interference using an 800 nm,50 fs femtosecond laser.The ultrafast dynamics of HSFL formation on the silicon surface of prefabricated LSFL under single femtosecond laser pulse irradiation were observed and analyzed for the first time using collinear pump-probe imaging method.In general,the evolution of the surface structure undergoes five sequential stages:the LSFL begins to split,becomes uniform HSFL,degenerates into an irregular LSFL,undergoes secondary splitting into a weakly uniform HSFL,and evolves into an irregular LSFL or is submerged.The results indicate that the local enhancement of the submerged nanocavity,or the nanoplasma,in the prefabricated LSFL ridge led to the splitting of the LSFL,and the thermodynamic effect drove the homogenization of the splitting LSFL,which evolved into HSFL.

Heat accumulation effects in femtosecond laser-induced subwavelength periodic surface structures on silicon

High-repetition rate femtosecond lasers are shown to drive heat accumulation processes that are attractive for femtosecond laser-induced subwavelength periodic surface structures on silicon.Femtosecond laser micromachining is no longer a nonthermal process,as long as the repetition rate reaches up to 100 kHz due to heat accumulation.Moreover,a higher repetition rate generates much better defined ripple structures on the silicon surface,based on the fact that accumulated heat raises lattice temperature to the melting point of silicon(1687 K),with more intense surface plasmons excited simultaneously.Comparison of the surface morphology on repetition rate and on the overlapping rate confirms that repetition rate and pulse overlapping rate are two competing factors that are responsible for the period of ripple structures.Ripple period drifts longer because of a higher repetition rate due to increasing electron density;however,the period of laser structured surface is significantly reduced with the pulse overlapping rate.The Maxwell–Garnett effect is confirmed to account for the ripple period-decreasing trend with the pulse overlapping rate.

Formation of Laser-Induced Periodic Surface Structures on Reaction-Bonded Silicon Carbide by Femtosecond Pulsed Laser Irradiation

Reaction-bonded silicon carbide(RB-SiC)is an excellent engineering material with high hardness,stiffness,and resistance to chemical wear.However,its widespread use is hindered due to the properties mentioned above,making it difficult to machine functional surface structures through mechanical and chemical methods.This study investigated the fundamental characteristics of laser-induced periodic surface structures(LIPSSs)on RB-SiC via femtosecond pulsed laser irradiation at a wavelength of 1028 nm.Low-spatial-frequency LIPSS(LSFL)and high-spatial-frequency LIPSS(HSFL)formed on the surface along directions perpendicular to the laser polarization.SiC grains surrounded by a large amount of Si show a reduced threshold for LIPSS formation.By varying laser fluence and scanning speed,HSFL-LSFL hybrid structures were generated on the SiC grains.Transmission electron microscopy observations and Raman spectroscopy were carried out to understand the formation mechanism of the hybrid LIPSS.A possible mechanism based on the generation of multiple surface electromagnetic waves due to the nonlinear response of SiC was proposed to explain the hybrid structure formation.Furthermore,the direction of laser scanning with respect to laser polarization affects the uniformity of the generated LIPSS.

Tuning the surface electronic structure of noble metal aerogels to promote the electrocatalytic oxygen reduction

The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts.Here,the surface electronic structure of Ptbased noble metal aerogels(NMAs)was modulated by various organic ligands,among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis.Theoretical calculations suggested the smaller energy barrier for the transformation of O^(*) to OH^(*) and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals,thus enhancing the ORR intrinsic activity.Both Pt3Ni and Pt Pd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media.Remarkably,the 4-methylphenylene modified Pt Pd aerogel exhibited the higher halfwave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C.This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.

Plowing-Extrusion Processes and Performance of Functional Surface Structures of Copper Current Collectors for Lithium-Ion Batteries

Most copper current collectors for commercial lithium-ion batteries(LIBs)are smooth copper foils,which cannot form a stable and effective combination with electrode slurry.They are likely to deform or fall off after long-term operation,resulting in a sharp decline in battery performance.What is worse is that this condition inevitably causes internal short circuits and thus brings about security risks.In this study,a process route of fabricating the functional surface structures on the surface of a copper collector for LIBs by twice-crisscross micro-plowing(TCMP)is proposed,which provides a new idea and an efficient method to solve the above problems from the perspective of manufacturing.The finite element simulation of TCMP combined with the cutting force test and morphological characterization is conducted to verify the forming mechanism of the surface structures on a copper sheet and its relationship with the processing parameters.The influence of several key processing parameters on the surface characteristics of the copper sheet is comprehensively explored.A series of functions is tested to obtain the optimal parameters for performance improvement of the current collector.Results show that the structured copper sheet with the cutting distance of 250μm,cutting depth of 80μm,and cutting crossing angle of 90°enables the best surface features of the current collector;the contact angle reaches 0°,the slurry retention rate is up to 89.2%,and the friction coefficient reaches 0.074.The battery using the as-prepared structured copper sheet as the current collector produces a specific capacity of 318.6 mAh/g after 50 cycles at a current density of 0.2 C,which is 132.7%higher than the one based on a smooth surface.The capacity reversibility of the sample with the new current collector is much better than that of the traditional samples,yielding a lower impedance.

STM study of In nanostructures formation on Ge(001) surface at different coverages and temperatures

Different In/Ge（001） nanostructures have been obtained by annealing the samples at 320℃ with different coverages of In. Annealing a sample with a critical coverage of 2.1 monolayer of In, different In/Ge（001） nanostructures can be obtained at different temperatures. It is found that thermal annealing treatments first make In atoms form elongated Ge{103}-faceted In-clusters, which will grow wider and longer with increasing temperature, and finally cover the surface completely.

Precisely monitoring and tailoring the surface structures of nanomaterials by in-situ electron microscopy

The transmission electron microscope(TEM)is now one of the most powerful tools for structural characterization due to its high spatial resolution,especially with the advent of the spherical aberration corrector.The interaction between electrons and specimens allows tailoring surface structures by electron irradiation.Furthermore,along with the development of special holders and specimen preparation techniques,the structural evolution of surfaces/interfaces can be dynamically monitored under external fields or reaction environments at the nanoscale,which promotes not only the establishment of the relationship between atomic structures and novel properties,but also potential applications in nanodevices.In this report,we review some of our recent results obtained by TEM,including dynamical observation of surface-mediated novel phenomena,controllable fabrication of nanostructures,and some potential applications in nanodevices.

Nanosecond laser-induced controllable periodical surface structures on silicon

In this paper,an effective method is proposed to generate specific periodical surface structures.A 532 nm linearly polarized laser is used to irradiate the silicon with pulse duration of 10 ns and repetition frequency of 10 Hz.Laser-induced periodic surface structures(LIPSSs) are observed when the fluence is 121 mJ/cm;and the number of pulses is 1000.The threshold of fluence for generating LIPSS gradually increases with the decrease of the number of pulses.In addition,the laser incident angle has a notable effect on the period of LIPSS,which varies from 430 nm to 1578 nm,as the incident angle ranges from10° to 60° correspondingly.Besides,the reflectivity is reduced significantly on silicon with LIPSS.

Periodic surface structures on Ni–Fe film induced by a single femtosecond laser pulse with diffraction rings

This Letter reports the formation of periodic surface structures on Ni–Fe film irradiated by a single femtosecond laser pulse. A concave lens with a focus length of-150 mm is placed in front of an objective（100×, NA=0.9）,which transforms the Gaussian laser field into a ring distribution by the Fresnel diffraction. Periodic ripples form on the ablation area after the irradiation of a single femtosecond laser pulse, which depends on the laser polarization and laser fluence. We propose that the ring structure of the laser field leads to a similar transient distribution of the permittivity on the sample surface, which further launches the surface plasmon polaritons. The interaction of the incident laser with surface plasmon polaritons dominates the formation of periodic surface structures.

Experimental research of laser-induced periodic surface structures in a typical liquid by a femtosecond laser

A constant elastic alloy is a widely used material with a high elastic modulus and an excellent wave velocity consistency. Different morphologies on the constant elastic alloy surface are observed through femtosecond laser irradiation. When the laser average fluence is set to 0.58 J∕cm^2 and 200 laser pulses, with the increasing depth of distilled water, the period of the laser-induced periodic surface structures（LIPSS） becomes shorter accordingly.The higher the ethanol concentration is, the more spot-shaped structures will be formed among the surface structures when the depth of the coverage of ethanol is 2 mm. The period of the LIPSS reaches its maximum when the concentration of ethanol is 80%.

Symmetry-breaking of LiMn_(6) hexatomic-ring in grain surface of Li_(2)MnO_(3)

LiMn_(6) hexatomic-rings act as functional units in Li-rich layered oxides(LLOs),which determine the capacity,voltage,and structural stability of LLOs.However,the symmetry of the LiMn_(6) hexatomic-ring is always broken,especially in the grain surface of LLOs,which will greatly affect its electrochemical performance.Herein,the symmetry-breaking of LiMn_(6) hexatomic-ring in the grain surface of Li_(2)MnO_(3) was studied,and their effect on charge compensation mechanism and structure evolution behavior was thoroughly investigated.The results show that the electrochemical activity of the symmetry-broken LiMn_(6) hexatomic-ring is higher than that of the unbroken LiMn_(6),and the former is more favorable for spinelization on the grain surface.Furthermore,the exposure proportion of crystallographic planes with different symmetry-broken LiMn_(6) hexatomic-ring has also been discussed,which can be adjusted by changing the partial pressure of oxygen.The in-depth understanding of the symmetry-breaking of LiMn_(6) hexatomic-ring will provide more targeted strategies for designing high-performance LLOs cathodes for lithium-ion batteries.

Tailoring the surface and interface structures of photocatalysts to enhance hydrogen production

Photocatalytic water splitting using semiconductor photocatalysts is a promising approach for the production of carbon-neutral,sustainable and clean hydrogen fuel.However,the separation and transport of photoinduced carriers are generally considered to be rate-limiting steps,and their low efficiency remains a major challenge.Therefore,much effort has been devoted to developing new strategies in surface/interface engineering of photocatalysts to improve the dynamics of charge separation/transport.This feature article briefly summarizes recent advances in photocatalyst surface/interface engineering by our research group,which have been achieved through the design of various novel photocatalysts,including interfacial modulation,heterostructure construction,heteroatom doping,single atom and diatom sites.The article is divided into three parts:first,we briefly introduce the three key processes involved in solar water splitting and reveal relationships between the properties of nanostructural photocatalysts and the fundamentals of water splitting;second,we detail methods and strategies for surface and interfacial structures to improve the efficiency of the fundamental processes,especially charge separation;finally,we explore prospects for photocatalytic water splitting applications.This article provides a valuable resource and strategies for researchers currently working in the field of photocatalytic water splitting.

Structural transformation of Ge dimers on Ge(001) surfaces induced by bias voltage

Scanning tunnelling microscopy is utilized to investigate the local bias voltage tunnelling dependent transformation between （2×1） and c（4×2） structures on Ge（001） surfaces, which is reversibly observed at room temperature and a critical bias voltage of -0.80 V. Similar transformation is also found on an epitaxial Ce islands but at a slightly different critical bias voltage of -1.00V. It is found that the interaction between the topmost atoms on the STM tip and the atoms of the dimers, and the pinning effect induced by Sb atoms, the nacancies or the epitaxial clusters, can drive the structural transformation at the critical bias voltage.

Laser-induced periodic surface structured electrodes with 45% energy saving in electrochemical fuel generation through field localization

Electrochemical oxidation/reduction of radicals is a green and environmentally friendly approach to generating fuels.These reactions,however,suffer from sluggish kinetics due to a low local concentration of radicals around the electrocatalyst.A large applied electrode potential can enhance the fuel generation efficiency via enhancing the radical concentration around the electrocatalyst sites,but this comes at the cost of electricity.Here,we report about a~45%saving in energy to achieve an electrochemical hydrogen generation rate of 3×10^(16) molecules cm^(–2)s^(–1)(current density:10 mA/cm^(2))through localized electric field-induced enhancement in the reagent concentration(LEFIRC)at laser-induced periodic surface structured(LIPSS)electrodes.The finite element model is used to simulate the spatial distribution of the electric field to understand the effects of LIPSS geometric parameters in field localization.When the LIPSS patterned electrodes are used as substrates to support Pt/C and RuO_(2) electrocatalysts,the η_(10) overpotentials for HER and OER are decreased by 40.4 and 25%,respectively.Moreover,the capability of the LIPSS-patterned electrodes to operate at significantly reduced energy is also demonstrated in a range of electrolytes,including alkaline,acidic,neutral,and seawater.Importantly,when two LIPSS patterned electrodes were assembled as the anode and cathode into a cell,it requires 330 mVs of lower electric potential with enhanced stability over a similar cell made of pristine electrodes to drive a current density of 10 mA/cm^(2).This work demonstrates a physical and versatile approach of electrode surface patterning to boost electrocatalytic fuel generation performance and can be applied to any metal and semiconductor catalysts for a range of electrochemical reactions.

Laser cleaning of steel structure surface for paint removal and repaint adhesion

Paint removal from steel structure is executed for shipyards of marine and offshore engineering.Due to environmental unfriendliness and unhealthy drawbacks of sand blasting technique, laser ablation technique is proposed as a substituting method.By absorbing high energy of the 1064 nm pulsed laser, the paint is vaporized quickly.The ablated debris is then collected by using a suction pump.Initial metal surface of the steel is exposed when laser beam irradiates perpendicularly and scans over it.The cleaned surface fulfills the requirements of surface preparation standards ISO 8501 of SA2.The adhesion is further characterized with pull-off test after carrying out painting with Jotamastic 87 aluminum paint.The repainting can be embedded onto the laser cleaned surface to bond much more tightly.The excellent adhesion strength of 20 MPa between repainted coating and the substrate is achieved, which is higher than what is required by shipyards applications.

Experimental Study on Wear Performance and Oil Film Characteristics of Surface Textured Cylinder Liner in Marine Diesel Engine

It is of a vital importance to reduce the frictional losses in marine diesel engines. Advanced surface textures have provided an e ective solution to friction performance of rubbing pairs due to the rapid development of surface engineering techniques. However,the mechanisms through which textured patterns and texturing methods prove beneficial remains unclear. To address this issue,the tribological system of the cylinder liner?piston ring(CLPR) is investigated in this work. Two types of surface textures(Micro concave,Micro V?groove) are processed on the cylinder specimen using di erent processing methods. Comparative study on the friction coe cients,worn surface texture features and oil film characteristics are performed. The results demonstrate that the processing method of surface texture a ect the performance of the CLPR pairs under the specific testing conditions. In addition the micro V?groove processed by CNCPM is more favorable for improving the wear performances at the low load,while the micro?con?cave processed by CE is more favorable for improving the wear performances at the high load. These findings are in helping to understand the e ect of surface texture on wear performance of CLPR.