Picosecond Laser Ablation Research Articles

Ni/Cu/Ag plated contacts: A study of resistivity and contact adhesion for crystalline-Si solar cells

Ni/Cu/Ag plated contacts were examined as an alternate to Ag screen printed contacts for silicon (Si) solar cell metallization. To realize a reliable contact for industrial applications, the contact resistance and its adhesion to Si substrates were evaluated. Si surface roughness by picosecond (ps) laser ablation of silicon-nitride (SiNx) antireflection coating (ARC) was done in order to prepare the patterns. The sintering process after Ni/Cu/Ag full metallization in the form of the post-annealing process was applied to investigate the contact resistivity and adhesion. A very low contact resistivity of approximately 0.5 mΩcm2 has been achieved with measurements made by the transfer length method (TLM). Thin finger lines of about 26 μm wide and a line resistance of 0.51 Ω/cm have been realized by plating technology. Improved contact adhesion by combining the ps-laser-ablation and post-annealing process has been achieved. We have shown the peel-off strengths >1 N/mm with a higher average adhesion of 1.9 N/mm. Our pull-tab adhesion tests demonstrate excellent strength well above the wafer breakage force.

Enhanced optical response of ZnO/Ag nanocolloids prepared by a picosecond laser

The photoluminescence (PL) of silver-decorated zinc oxide (ZnO/Ag) nanocolloids synthesized by picosecond laser ablation in water was studied. Compared to ZnO, a significant enhancement of the broad near-ultraviolet PL luminescence peak is observed in the presence of Ag nanoparticles (NPs), as well as changes in the broad multi-component visible emission feature. The comparative discussion of the chemical and structural analyses suggests that the high electric field in proximity of the Ag NPs gives rise to an enhancement of the ZnO exciton oscillator strength. Optical coupling results in the increase of spontaneous emission rate and internal quantum efficiency of the Ag-decorated ZnO nanostructures. The presented results are helpful for the design of innovative and highly performing LED devices with spatially uniform output.

High-temperature imprinting and superhydrophobicity of micro/nano surface structures on metals using molds fabricated by ultrafast laser ablation

Micro/nano surface structures show great significance in both fundamental research and practical applications. Imprinting technique is widely used to fabricate micro/nano surface structures on polymers at low temperature, but barely implemented on metals. In this paper, femtosecond (fs) laser was used to fabricate micro/nano surface structures on tungsten (W), which served as molds for subsequent solid state imprinting process to replicate the counter structures onto copper (Cu) surface at temperature up to 1000°C. Nano-ripples superimposed on micro-bumps array are fabricated without surface oxidation, and the height of the micro-bumps is adjustable by varying the laser energy input for W molds preparation. The as-prepared Cu surface structures are hydrophobic and turn to superhydrophobic after chemical modification. To demonstrate the feasibility and capability of this technique, similar surface structures were fabricated on A356 aluminum alloy (A356 AA) by liquid state imprinting at 740°C using M2 steel molds prepared by picosecond (ps) laser ablation. This approach combines the advantages of ultrafast laser ablation to fabricate molds with micro/nano surface structures and high-temperature imprinting process to replicate the micro/nano structures onto target metallic surfaces. It opens new possibility for the mass fabrication of functional micro/nano surface structures on metals.

Influence of the ARC patterning method and annealing on the contact adhesion of Ni/Cu-plated solar cells

Ni/Cu two-step plating is a promising metallization technique because low contact resistance and improved contact adhesion can be achieved after the Ni annealing process. Also, narrow fingers, which are required for high-efficiency solar cells, can be formed by plating. However, the reliability of contact adhesion is still considered one obstacle to industrializing solar cells with plated metal contacts. In this experiment, the influence of ARC opening methods on plated contact adhesion was investigated because the roughnesses of the Si surfaces produced by using pico-second laser ablation and photolithography may be different. Also, the annealing process was conducted before and after plating Cu/Ag metal stacks. The sequence of the annealing can be significant for efficient production because plating is a wet process while annealing is a dry process. The contact adhesion was measured by using a peel-off test. The test was conducted on a 1.5-mm-wide by a 60 ~ 70- mm-long bus bar area. A 3.2-N/mm adhesion force was recorded as a highest average value along the bus bar.

The characteristics of novel bimodal Ag–TiO2 nanoparticles generated by hybrid laser-ultrasonic technique

Silver–titania (Ag–TiO2) nanoparticles with smaller Ag nanoparticles attached to larger TiO2 nanoparticles were generated by hybrid ultrasonic vibration and picosecond laser ablation of Ag and Ti bulk targets in deionised water, for the first time. The laser has a wavelength of 1064 nm and a pulse duration of 10 ps. It was observed that without the ultrasonic vibration, Ag and TiO2 nanoparticles did not combine, thus the role of ultrasonic vibration is essential. In addition, colloidal TiO2 and Ag nanoparticles were generated separately for comparison under the same laser beam characteristics and process conditions. The absorption spectra of colloidal Ag–TiO2 cluster nanoparticles were examined by UV–Vis spectroscopy, and size distribution was characterised using transmission electron microscopy. The morphology and composition of Ag–TiO2 nanoparticles were examined using scanning transmission electron microscopy in high-angle annular dark field, and energy-dispersive X-ray spectroscopy. The crystalline structures were investigated by X-ray diffraction. The size of larger TiO2 particles was in the range 30–150 nm, and the smaller-sized Ag nanoparticles attached to the TiO2 was mainly in the range of 10–15 nm. The yield is more than 50 % with the remaining nanoparticles in the form of uncombined Ag and TiO2. The nanoparticles generated had strong antibacterial effects as tested against E. coli. A discussion is given on the role of ultrasonic vibration in the formation of Ag–TiO2 hybrid nanoparticles by picosecond laser ablation.

Size of silver nanoparticles determines proliferation ability of human circulating lymphocytes in vitro.

In this work we present biological effects of silver nanoparticles (AgNPs) synthesized by picosecond laser ablation of silver in deionized water. We examined induction of chromosomal aberrations, lymphocyte micronuclei, appearance and recovery of double strand breaks (DSBs) of DNA, cell proliferation potential, concentration of lipid peroxidation products and insulin-like growth factor 1 (ILGF-1). We found that AgNPs sized from 3 nm to 8 nm induce cell cytostasis, which is accompanied with its clastogenic action on DNA, while AgNPs, sized 2 nm behaves contrary stimulating cell proliferation by enhancing ILGF-1 concentration.

Debris-free rear-side picosecond laser ablation of thin germanium wafers in water with ethanol

In this paper, we perform liquid-assisted picosecond laser cutting of 150μm thin germanium wafers from the rear side. By investigating the cutting efficiency (the ability to allow an one-line cut-through) and quality (characterized by groove morphologies on both sides), the pros and cons of this technique under different conditions are clarified. Specifically, with laser fluence fixed, repetition rate and scanning speed are varied to show quality and efficiency control by means of laser parameter modulation. It is found that low repetition rate ablation in liquid gives rise to a better cut quality on the front side than high repetition rate ablation since it avoids dispersed nanoparticles redeposition resulting from a bubble collapse, unlike the case of 100kHz which leads to large nanorings near the grooves resulting from a strong interaction of bubbles and the case of 50kHz which leads to random cutting due to the interaction of the former pulse induced cavitation bubble and the subsequent laser pulse. Furthermore, ethanol is mixed with pure distilled water to assess the liquid's impact on the cutting efficiency and cutting quality. The results show that increasing the ethanol fraction decreases the ablation efficiency but simultaneously, greatly improves the cutting quality. The improvement of cut quality as ethanol ratio increases may be attributed to less laser beam interference by a lower density of bubbles which adhere near the cut kerf during ablation. A higher density of bubbles generated from ethanol vaporization during laser ablation in liquid will cause stronger bubble shielding effect toward the laser beam propagation and therefore result in less laser energy available for the cut, which is the main reason for the decrease of cut efficiency in water–ethanol mixtures. Our findings give an insight into under which condition the rear-side laser cutting of thin solar cells should be performed: high repetition, pure distilled water and high laser power are favorable for high-speed rough cutting but the cut kerf suffers from strong side effects of ripples, nanoredeposition occurrence, while low laser power at low repetition rate (10kHz), mixed solution (1wt% ethanol in water) and moderate scanning speed (100μm/s) are preferable for ultrafine high-quality debris-free cutting. The feasibility of high-quality cut is a good indication of using rear laser ablation in liquid to cut thinner wafers. More importantly, this technique spares any post cleaning steps to reduce the risk to the contamination or crack of the thin wafers.

Influence of an Angular Hatching Exposure Strategy on the Surface Roughness During Picosecond Laser Ablation of Hard Materials

Innovative chip breakers for cutting tools made of very hard materials require laser ablation and demand a high quality regarding the manufactured surface. When processing materials such as polycrystalline cubic boron-nitride or tungsten carbide the surface roughness by laser ablation reaches Sa = 1,0-2,9 μm compared to Sa = 0,42 μm achieved by grinding. Therefore in the presented research the influence of the hatching exposure strategy on surface roughness during picosecond laser ablation of tungsten carbide is examined. The areal, layerwise ablation process is separated into its elements which are represented by intersection zones between single and multiple laser vectors. Thus two mechanisms of roughness formation are identified and described by model functions. Further the mechanisms are transferred to areal ablation in which surface roughness decreases due to improved hatching angles compared to a commonly used one of φ= 0°/90°. With this approach the roughness is reduced by approximately factor 2,0-3,5 to Sa = 0,82 μm. In conclusion guidelines are derived which present favorable settings for high quality laser ablation processes.

Ultrasmall, Ligand-Free Ag Nanoparticles with High Antibacterial Activity Prepared by Pulsed Laser Ablation in Liquid

Since ancient times, silver and its compounds have been known to have a broad spectrum of antimicrobial activities for bacteria, fungi, and viruses. Due to the increasing bacterial resistance to classic antibiotics, the investigations of Ag NPs have increased. Herein, we present the preparation of ligand-free Ag NPs with 3 and 20 nm sizes by applying picosecond laser ablation in liquid at 355 and 1065 nm. Our laser processing system allows a high control on particle sizes. The produced nanoparticles were characterized by means of transmission electron microscopy, UV-Vis spectroscopy, and X-ray diffraction. The size effect on the antibacterial activity of Ag NPs was tested againstE. coliandS. aureus. The growth curves of bacteria were monitored at 0–5 mg/L of Ag NPs by a multimode microplate reader. The size effects as well as the concentration of Ag NPs on their antibacterial activity are discussed.

Study on hierarchical structured PDMS for surface super-hydrophobicity using imprinting with ultrafast laser structured models

We report a simple and inexpensive method for producing super-hydrophobic surfaces through direct replication of micro/nano-structures on polydimethylsiloxane (PDMS) from a replication master prepared by ultrafast-laser texturing process. Gratings were obtained on 304L stainless steel plate using picosecond laser ablation. It has been used as a master with grating areas of different structural features. PDMS negative replica was prepared from the masters, and PDMS positive replica was prepared from the negative replica thereafter. Wettability of samples of the steel master, negative and positive replicas was distinguished using the apparent contact angle (CA) of water drop. Relationships between the CAs on three kinds of samples and structural features were presented. Super-hydrophobic behavior with self-cleaning, exhibited by a water contact angle of 164.5° and sliding angle of 8.44°, was observed on the PDMS negative replica surface. The negative and positive replicas were sputtered on gold films, which were used to metalized PDMS and eliminate the submicron/nano-structures in hierarchical structures. Results prove that submicro/nano-structures of hierarchical structures enhance the hydrophobicity of material surface remarkably. This replication method can be applied for large scale production of micro/nano textured super-hydrophobic surfaces for commercial applications.

Sequential laser and ultrasonic wave generation of TiO2@Ag core-shell nanoparticles and their anti-bacterial properties

Core-shell nanoparticles have unusual physical, chemical and biological properties. Until now, for the Ag and TiO2 combination, only Ag core and TiO2 shell nanoparticles have been practically demonstrated. In this investigation, novel TiO2@Ag core-shell (TiO2 core and Ag shell) nanoparticles were produced via ultrasonic vibration of Ag-TiO2 compound nanoparticles. A bulk Ti/Ag alloy plate was used to generate colloidal Ag-TiO2 compound nanoparticles via picosecond laser ablation in deionised water. The colloidal nanoparticles were then sonicated in an ultrasonic bath to generate TiO2@Ag core-shell nanoparticles. They were characterised using a UV-VIS spectrometer, transmission electron microscopy (TEM), high-angle annular dark-field-Scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The Ag-TiO2 compound and the TiO2@Ag core-shell nanoparticles were examined for their antibacterial activity against Escherichia coli (E. coli) JM109 strain bacteria and compared with those of Ag and TiO2 nanoparticles. The antibacterial activity of the core-shell nanoparticles was slightly better than that of the compound nanoparticles at the same concentration under standard laboratory light conditions and both were better than the TiO2 nanoparticles but not as good as the Ag nanoparticles.

Study of dye sensitized solar cells based on ZnO photoelectrodes deposited by laser ablation and doctor blade methods

Dye sensitized solar cells (DSSCs) based on ZnO photoelectrodes deposited by picosecond laser ablation and doctor blade methods are studied. For deposition of ZnO photoelectrodes by laser ablation, a picosecond Nd:YVO4 laser (8ps, 50kHz, 532nm, 0.17J/cm2) was used. Depositions were made starting from a Zn pure target on fluorine doped tin oxide (FTO) substrate, in oxygen atmosphere at 10sccm gas flow rate at room temperature (RT). After deposition, the films were subjected to an annealing treatment at 400°C in oxygen for 2h. For deposition of ZnO photoelectrodes by doctor blade method, ZnO paste using ZnO nanoparticles (MK Impex Corp. 99.9%, 20nm) was prepared. The influence of the ZnO photoelectrodes, prepared by the two different methods, on the performances of the dye sensitized solar cells was investigated.The ZnO photoelectrodes prepared by both methods were investigated from morphostructural point of view. The optimum parameters of the films deposited by laser ablation which to correspond to the best efficiency of the cells were: 450mTorr oxygen pressure, with 5.83μm film thickness, delivering 580mV open circuit voltage (Voc), 1.16mA/cm2 short circuit current density (Jsc), 33% fill factor (FF), 0.22% conversion efficiency (ƞ). Concerning the ZnO photoelectrodes deposited by doctor blade method, almost a double value for ƞ was obtained of 0.43%, 25μm film thickness, 483mV Voc, 2.52mA/cm2 and 36% (FF).

Studies on linear, nonlinear optical and excited state dynamics of silicon nanoparticles prepared by picosecond laser ablation

We report results from our studies on the fabrication and characterization of silicon (Si) nanoparticles (NPs) and nanostructures (NSs) achieved through the ablation of Si target in four different liquids using ∼2 picosecond (ps) pulses. The consequence of using different liquid media on the ablation of Si target was investigated by studying the surface morphology along with material composition of Si based NPs. The recorded mean sizes of these NPs were ∼9.5 nm, ∼37 nm, ∼45 nm and ∼42 nm obtained in acetone, water, dichloromethane (DCM) and chloroform, respectively. The generated NPs were characterized by selected area electron diffraction (SAED), high resolution transmission microscopy (HRTEM), Raman spectroscopic techniques and Photoluminescence (PL) studies. SAED, HRTEM and Raman spectroscopy data confirmed that the material composition was Si NPs in acetone, Si/SiO2 NPs in water, Si-C NPs in DCM and Si-C NPs in chloroform and all of them were confirmed to be polycrystalline in nature. Surface morphological information of the fabricated Si substrates was obtained using the field emission scanning electron microscopic (FESEM) technique. FESEM data revealed the formation of laser induced periodic surface structures (LIPSS) for the case of ablation in acetone and water while random NSs were observed for the case of ablation in DCM and chloroform. Femtosecond (fs) nonlinear optical properties and excited state dynamics of these colloidal Si NPs were investigated using the Z-scan and pump-probe techniques with ∼150 fs (100 MHz) and ∼70 fs (1 kHz) laser pulses, respectively. The fs pump-probe data obtained at 600 nm consisted of single and double exponential decays which were tentatively assigned to electron-electron collisional relaxation (<1 ps) and non-radiative transitions (>1 ps). Large third order optical nonlinearities (∼10−14 e.s.u.) for these colloids have been estimated from Z-scan data at an excitation wavelength of 680 nm suggesting that the colloidal Si NPs find potential applications in photonic devices.

Laser-induced changes in titanium by femtosecond, picosecond and millisecond laser ablation

In order to realize the qualitative control of the laser-induced changes trend and the quantitative control of the laser-induced changes range in titanium upon laser irradiation with different pulse duration, comparative ablation experiments by femtosecond, picosecond and millisecond pulsed lasers were carried out on titanium in this study. Then the final surface morphology, aspect ratio, chemical composition and microstructural state of the ablated titanium were analyzed by laser scanning confocal microscopy, X-ray photoelectron spectroscopy and transmission electron microscopy, respectively. The dependency of the morphology, size, composition and microstructure of ablated titanium on laser pulse duration variation were emphatically discussed. It is found that, as the laser pulse duration increases from femtosecond to millisecond scale, surface morphology quality of ablated titanium gets worse, aspect ratio of microgroove decreases, proportion of titanium oxides in final ablation products becomes larger and the microstructural state of ablated titanium has a higher amorphization degree, which can be attributed to the decreased laser intensity per pulse and enhanced heat conduction effect in titanium with the pulse duration increasing.

Comparison of the Production of Nanostructures on Bulk Metal Samples by Picosecond Laser Ablation at Two Wavelengths for the Fabrication of Low-reflective Surfaces

Comparison of the Production of Nanostructures on Bulk Metal Samples by Picosecond Laser Ablation at Two Wavelengths for the Fabrication of Low-reflective Surfaces

Ag nanoparticles obtained by pulsed laser ablation in water: surface properties and SERS activity

We studied the surface properties and reactivity of silver nanoparticles obtained by picosecond or nanosecond pulsed laser ablation in water and with 1064‐nm wavelength. Ultraviolet–visible spectroscopy results and subsequent modelling by Mie theory indicated the presence of an oxide layer on the nanoparticle surface, which favours the colloidal stability, but reduces the interaction with the environment. The oxide layer is also responsible for the reduced surface enhanced Raman spectroscopy (SERS) activity of these colloids with respect to those obtained by chemical reduction. However, SERS activation can be efficiently obtained by addition of chloride ions to the colloids, leading to SERS enhancement factors that are comparable with those of the chemically prepared counterparts. Copyright © 2015 John Wiley & Sons, Ltd.

Elemental fractionation in 785 nm picosecond and femtosecond laser ablation inductively coupled plasma mass spectrometry

Elemental fractionation and ICP-MS signal response were investigated for two different pulse width laser beams originating from the same laser system. Femtosecond and picosecond laser beams at pulse widths of 130fs and 110ps, respectively, and wavelength of 785nm were used to ablate NIST 610 synthetic glass and SRM 1107 Naval Brass B at the same spot for 800 to 1000 laser pulses at different repetition rates (5 to 50Hz). Elemental fractionation was found to depend on repetition rate and showed a trend with femtosecond laser ablation that is opposite to that observed in picosecond laser ablation for most measured isotopes. ICP-MS signal intensity was higher in femtosecond than picosecond LA-ICP-MS in both NIST 610 and naval brass when ablation was conducted under the same fluence and repetition rate. The differences in signal intensity were partly related to differences in particle size distribution between particles generated by femtosecond and picosecond laser pulses and the consequent differences in transport and ionization efficiencies. The main reason for the higher signal intensity resulting from femtosecond laser pulses was related to the larger crater sizes compared to those created during picosecond laser ablation. Elemental ratios measured using 66Zn/63Cu, 208Pb/238U, 232Th/238U, 66Zn/232Th and 66Zn/208Pb were found to change with the number of laser pulses with data points being more scattered in picosecond than femtosecond laser pulses. Reproducibility of replicate measurements of signal intensities, fractionation and elemental ratios was better for fs-LA-ICP-MS (RSD ~3 to 6%) than ps-LA-ICP-MS (RSD ~7 to 11%).

Rear-side picosecond laser ablation of indium tin oxide micro-grooves

A comparative study of the fabrication of micro-grooves in indium tin oxide films by picosecond laser ablation for application in thin film solar cells is presented, evaluating the variation of different process parameters. Compared with traditional front-side ablation, rear-side ablation results in thinner grooves with varying laser power at a certain scan speed. In particular, and in contrast to front-side ablation, the width of the micro-grooves remains unchanged when the scan speed was changed. Thus, the micro-groove quality can be optimized by adjusting the scan speed while the groove width would not be affected. Furthermore, high-quality micro-grooves with ripple free surfaces and steep sidewalls could only be achieved when applying rear-side ablation. Finally, the formation mechanism of micro-cracks on the groove rims during rear-side ablation is analyzed and the cracks can be almost entirely eliminated by an optimization of the scan speed.

The mechanism and process of nanosecond pulsed-laser induced subwavelength periodic ripples on silica films

The discovery of subwavelength periodic ripples with similar grating structures is currently mainly associated with femto-/picosecond laser ablation experiments. A nanosecond laser is generally accepted as incapable of etching subwavelength periodic ripples. Recently, the subwavelength periodic ripples on the surface of silica films induced by nanosecond laser pulses have been observed. In this paper, theoretical models have been established to interpret the formation process of subwavelength periodic ripples etched by nanosecond pulsed laser, and some key questions have been discussed.

Generation of silver titania nanoparticles from an Ag–Ti alloy via picosecond laser ablation and their antibacterial activities

In this work, a bulk Ti/Ag alloy was used, for the first time, to produce Ag–TiO2 compound nanoparticles using picosecond laser ablation in deionised water.