Pulsed Laser Fragmentation Research Articles

Pulsed laser fragmentation synthesis of carbon quantum dots (CQDs) as fluorescent probes in non-enzymatic glucose detection

Pulsed laser fragmentation in liquid (PLFL) is one of the synthesis routes for producing high-purity carbon quantum dots (CQDs) with less toxic by-products in a straightforward system. The limited literature regarding the application of PLFL-synthesized CQDs motivated this study to exploit them as fluorescent probes in glucose sensing. The design of a fluorescent-based non-enzymatic glucose sensor was achieved by implementing CQDs and 3-aminophenylboronic acid (APBA) as fluorescent probes and glucose receptors, respectively. The CQDs were fabricated by PLFL through an Nd:YAG nanosecond laser, starting from the carbon powder dispersion in ethanol. Then, a laser-assisted post-modification process with oxidizing acid was implemented to produce water-dispersible CQDs for easy functionalization. Functionalizing these CQDs with APBA (CQDs-APBA) resulted in a blue-shifted fluorescence emission with a 35% quantum yield and high photostability. The CQDs-APBA exhibited a turn-off response at increasing glucose concentrations. This method offers good sensitivity with a linear detection range of glucose with a concentration of 0.165 to 8 mM and a detection limit of 165 µM. The applicability of this sensor to real analytes such as saliva obtained a satisfactory result with good reproducibility. This work proves that CQDs synthesized from PLFL can also be an alternative fluorescent probe for fluorescent-based sensing applications.

Laser Fragmentation of Green Tea-synthesized Silver Nanoparticles and Their Blood Toxicity: Effect of Laser Wavelength on Particle Diameters.

The efficacy of fractionation is significantly impacted by the colloidal particles' spontaneous absorption of laser beam radiation. The classification of silver nanoparticles during fragmentation processing is regulated through the collection of a combination of laser pulses with wavelengths of 1064 nm and 532 nm. This study presents an investigation of the efficacy of a plant extract in conjunction with the incorporation of supplementary silver nanoparticles, as well as the generation of smaller-sized silver nanoparticles using laser fragmentation.and then measure thier toxity on the blood. Ag nanoparticles were synthesized using pulsed laser fragmentation on green tea AgNPs. The synthesis process involved the utilization of a Q-switch Nd:YAG laser with wavelengths of 1064 nm and 532 nm, with energy ranging from 200 to 1000 mJ. Initially, a silver nano colloid was synthesized through the process of fragmented of the Ag target using the second harmonic generation of 532 nm at various energy levels. The optimal energy within the selected wavelengths was determined in order to facilitate the ultimate comparison. Transmission electron microscopy (TEM) was used to determine surface morphology and average particle size, while a spectrophotometer was used to analyses UV light's spectrum characteristics. The measurements focused on the surface plasmon resonance (SPR) phenomenon. The absorption spectra of silver nanoparticles exhibit distinct and prominent peaks at wavelengths of 405 nm and 415 nm. The mean diameter of the silver nanoparticles was found to be 16 nm and 20 nm, corresponding to wavelengths of 1064 nm and 532 nm, respectively. As a consequence, there is a decrease in the range of particle sizes and a decrease in the mean size to lower magnitudes, resulting in a very stable colloid. This particular methodology has demonstrated considerable efficacy in the production of colloidal suspensions with the intended particle dimensions. Moreover, by the analysis of nanoparticles in human blood, no discernible alterations in the blood constituents were seen, indicating their non-toxic nature.

Molecular Dynamics Modeling of Pulsed Laser Fragmentation of Solid and Porous Si Nanoparticles in Liquid Media.

The production of non-toxic and homogeneous colloidal solutions of nanoparticles (NPs) for biomedical applications is of extreme importance nowadays. Among the various methods for generation of NPs, pulsed laser ablation in liquids (PLAL) has proven itself as a powerful and efficient tool in biomedical fields, allowing chemically pure silicon nanoparticles to be obtained. For example, laser-synthesized silicon nanoparticles (Si NPs) are widely used as contrast agents for bio visualization, as effective sensitizers of radiofrequency hyperthermia for cancer theranostics, in photodynamic therapy, as carriers of therapeutic radionuclides in nuclear nanomedicine, etc. Due to a number of complex and interrelated processes involved in the laser ablation phenomenon, however, the final characteristics of the resulting particles are difficult to control, and the obtained colloidal solutions frequently have broad and multimodal size distribution. Therefore, the subsequent fragmentation of the obtained NPs in the colloidal solutions due to pulsed laser irradiation can be utilized. The resulting NPs' characteristics, however, depend on the parameters of laser irradiation as well as on the irradiated material and surrounding media properties. Thus, reliable knowledge of the mechanism of NP fragmentation is necessary for generation of a colloidal solution with NPs of predesigned properties. To investigate the mechanism of a laser-assisted NP fragmentation process, in this work, we perform a large-scale molecular dynamics (MD) modeling of FS laser interaction with colloidal solution of Si NPs. The obtained NPs are then characterized by their shape and morphological properties. The corresponding conclusion about the relative input of the properties of different laser-induced processes and materials to the mechanism of NP generation is drawn.

Nanostructured SnS-Si hybrid photodetectors by pulsed laser processed nanocolloids

This research investigates the fabrication of SnS-Si hybrids for photodetection and photocatalysis using nanocolloids of tin sulfide (SnS), monocrystalline silicon (Sim) and polycrystalline silicon (Sip) produced by laser-assisted techniques (pulsed laser fragmentation as well as ablation in liquid). Characterization of the nanocolloids and the hybrid thin films obtained by techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron Spectroscopy (XPS), Raman spectroscopy, UV–Visible spectroscopy and photoluminescence spectroscopy (PL) are presented in this work. Post-deposition annealing improved the material properties of the hybrid films and the films exhibited optical bandgaps between 1.51 and 1.68 eV, suitable for light detection. In the case of hybrid SnS-Si films, SnS-Sim showed two orders of current higher than the SnS-Sip films. The photocurrent dynamic curves (current vs time) and current-voltage (I–V) characteristics are investigated to verify the improved device performances. The photodetector parameters such as sensitivity, responsivity, detectivity are also reported. Compared with conventional SnS thin film devices, all the films (SnS and SnS-Si hybrids) in this work responded to illumination sources of wavelengths up to 1064 nm. This is one of the initial studies on hybrid devices with Si nanoparticles for photodetector applications. All the films showed ultra-short response/recovery times in the range of 400–800 ms and their photodetector parameters were recorded. The films demonstrated good stability and cyclic photocatalytic activity to visible light.

Laser-generated nanoparticles from Fe-based metallic glass in water and its amorphization control by pulsed laser processing

The laser synthesis and processing of colloids represents a group of scalable and “green” synthesis methods of crystalline metal oxides, that have recently made encouraging progresses in preparing amorphous as well as defect-rich nanoparticles. The relevant conditions and mechanisms that allow the design of amorphous metal oxides (AMOs) remain unknown. Consequently, in this work the synthesis of Fe-based partially amorphous oxide nanoparticles (NPs) by pulsed laser ablation in water was studied. Furthermore, both laser pulse duration and the number of laser pulse in pulsed laser fragmentation in liquid (LFL) allow a precise control of amorphization of AMOs in water. Hereby, a high-fluence nanosecond-LFL provides a significantly higher amorphization rate, whereas picosecond-LFL always presents minor fractions of crystalline α-Fe even with a higher specific energy input and laser intensity. Consequently, the laser fluence required for the repeated melting and quenching of NP appears to be the decisive parameter to control amorphization. During laser synthesis and processing of colloids, the amorphization of AMOs appears to be linked to the apparent size reduction effect, while a complete full amorphization of AMOs may be attributed to the stronger oxidation effects. This work will stimulate future studies using laser-generated AMO NPs for further functional purposes.

Photomechanical Laser Fragmentation of IrO2 Microparticles for the Synthesis of Active and Redox-Sensitive Colloidal Nanoclusters.

Pulsed laser fragmentation of microparticles (MPs) in liquid is a synthesis method for producing high-purity nanoparticles (NPs) from virtually any material. Compared with laser ablation in liquids (LAL), the use of MPs enables a fully continuous, single-step synthesis of colloidal NPs. Although having been employed in several studies, neither the fragmentation mechanism nor the efficiency or scalability have been described. Starting from time-resolved investigations of the single-pulse fragmentation of single IrO2 MPs in water, the contribution of stress-mediated processes to the fragmentation mechanism is highlighted. Single-pulse, multiparticle fragmentation is then performed in a continuously operated liquid jet. Here, 2nm-sized nanoclusters (NCs) accompanied by larger fragments with sizes ranging between several ten nm and several µm are generated. For the nanosized product, an unprecedented efficiency of up to 18µgJ-1 is reached, which exceeds comparable values reported for high-power LAL by one order of magnitude. The generated NCs exhibit high catalytic activity and stability in oxygen evolution reactions while simultaneously expressing a redox-sensitive fluorescence, thus rendering them promising candidates in electrocatalytic sensing. The provided insights will pave the way for laser fragmentation of MPs to become a versatile, scalable yet simple technique for nanomaterial design and development.

Au-Ag Alloy Nanocorals with Optimal Broadband Absorption for Sunlight-Driven Thermoplasmonic Applications.

Noble metal nanoparticles are efficient converters of light into heat but typically cover a limited spectral range or have intense light scattering, resulting in unsuited for broadband thermoplasmonic applications and sunlight-driven heat generation. Here, Au–Ag alloy nanoparticles were deliberately molded with an irregular nanocoral (NC) shape to obtain broadband plasmon absorption from the visible to the near-infrared yet at a lower cost compared to pure Au nanostructures. The Au–Ag NCs are produced through a green and scalable methodology that relies on pulsed laser fragmentation in a liquid, without chemicals or capping molecules, leaving the particles surface free for conjugation with thiolated molecules and enabling full processability and easy inclusion in various matrixes. Numerical calculations showed that panchromism, i.e., the occurrence of a broadband absorption from the visible to the near-infrared region, is due to the special morphology of Au–Ag alloy NCs and consists of a purely absorptive behavior superior to monometallic Au or Ag NCs. The thermoplasmonic properties were assessed by multiwavelength light-to-heat conversion experiments and exploited for the realization of a cellulose-based solar-steam generation device with low-cost, simple design but competitive performances. Overall, here it is shown how laser light can be used to harvest solar light. Besides, the optimized broadband plasmon absorption, the green synthetic procedure, and the other set of positive features for thermoplasmonic applications of Au–Ag NCs will contribute to the development of environmentally friendly devices of practical utility in a sustainable world.

Maghemite nanoparticles decorated semiconducting graphitic carbon nitride hetero-structured nanocomposite: Facile synthesis, characterizations and its visible light active photocatalytic system for removal of hazardous organic pollutants from aqueous solutions

Hetero-structured nanocomposite consisting of graphitic carbon nitride host, decorated by γ-phase iron oxide, maghemite (γ-Fe2O3@G-CN) was synthesized in different mass contents of γ-Fe2O3 (5%, 10% and 20%) in the composite, by the method of nanosecond pulsed laser fragmentation, and defect engineering in liquid for the removal of hazardous organic pollutants from aqueous solutions. The elemental, structural, and morphological characterizations of the synthesized nanocomposites by XPS, XRD, TEM, and HR-TEM exhibited the proper anchoring of γ-Fe2O3 on the graphitic carbon nitride polymeric network. Also, the diffuse reflectance spectra, and the room temperature photoluminescence spectra respectively revealed that the presence of γ-Fe2O3 in graphitic carbon nitride brought about the enhanced and extended visible light absorption, and reduced recombination of photo induced electron hole pairs, the characteristics desired in a good photo-catalyst. Moreover, this composite material exhibited the z-scheme photo catalytic mechanism, where the more energetic electrons and holes in the composite band structure mediate the redox reaction in the photo-catalysis. The photo-catalytic efficiency of γ-Fe2O3@G-CN nanocomposite was evaluated in the photo-catalytic degradation of methyl blue (MB), and rhodamine-B (Rh-B) cationic dyes under visible light irradiations. For both the degradation processes, all the variants of γ-Fe2O3@G-CN nanocomposite consistently showed the enhanced photocatalytic efficiency with respect to pure GCN, with the maximum efficiency recorded for 10% γ-Fe2O3 in γ-Fe2O3@G-CN nanocomposite.

Size Control of Synthesized Silver Nanoparticles by Simultaneous Chemical Reduction and Laser Fragmentation in Origanum majorana Extract: Antibacterial Application.

In this work, silver nanoparticles (Ag NPs) were synthesized using a chemical reduction approach and a pulsed laser fragmentation in liquid (PLFL) technique, simultaneously. A laser wavelength of 532 nm was focused on the as produced Ag NPs, suspended in an Origanum majorana extract solution, with the aim of controlling their size. The effect of liquid medium concentration and irradiation time on the properties of the fabricated NPs was studied. While the X-ray diffraction (XRD) pattern confirmed the existence of Ag NPs, the UV–Vis spectrophotometry showed a significant absorption peak at about 420 nm, which is attributed to the characteristic surface plasmon resonance (SPR) peak of the obtained Ag NPs. By increasing the irradiation time and the Origanum majora extract concentration, the SPR peak shifted toward a shorter wavelength. This shift indicates a reduction in the NPs’ size. The effect of PLFL on size reduction was clearly revealed from the transmission electron microscopy images. The PLFL technique, depending on experimental parameters, reduced the size of the obtained Ag NPs to less than 10 nm. The mean zeta potential of the fabricated Ag NPs was found to be greater than −30 mV, signifying their stability. The Ag NPs were also found to effectively inhibit bacterial activity. The PLFL technique has proved to be a powerful method for controlling the size of NPs when it is simultaneously associated with a chemical reduction process.

Design and perspective of amorphous metal nanoparticles from laser synthesis and processing.

Amorphous metal nanoparticles (A-NPs) have aroused great interest in their structural disordering nature and combined downsizing strategies (e.g. nanoscaling), both of which are beneficial for highly strengthened properties compared to their crystalline counterparts. Conventional synthesis strategies easily induce product contamination and/or size limitations, which largely narrow their applications. In recent years, laser ablation in liquid (LAL) and laser fragmentation in liquid (LFL) as "green" and scalable colloid synthesis methodologies have attracted extensive enthusiasm in the production of ultrapure crystalline NPs, while they also show promising potential for the production of A-NPs. Yet, the amorphization in such methods still lacks sufficient rules to follow regarding the formation mechanism and criteria. To that end, this article reviews amorphous metal oxide and carbide NPs from LAL and LFL in terms of NP types, liquid selection, target elements, laser parameters, and possible formation mechanism, all of which play a significant role in the competitive relationship between amorphization and crystallization. Furthermore, we provide the prospect of laser-generated metallic glass nanoparticles (MG-NPs) from MG targets. The current and potential applications of A-NPs are also discussed, categorized by the attractive application fields e.g. in catalysis and magnetism. The present work aims to give possible selection rules and perspective on the design of colloidal A-NPs as well as the synthesis criteria of MG-NPs from laser-based strategies.

Graphene Quantum Dots: Fundamental Understanding of the Formation Mechanism for Graphene Quantum Dots Fabricated by Pulsed Laser Fragmentation in Liquid: Experimental and Theoretical Insight (Small 38/2020)

The pulsed laser fragmentation in liquid (PLFL) process is a promising technique for the synthesis of carbon‐based functional materials. However, a fundamental deep understanding of the formation of graphene quantum dots (GQDs) from multiwalled carbon nanotubes (MWCNTs) by PLFL has still not been achieved despite the high demand. In article number 2003538, Jeong Ho Ryu, Hyuksu Han, Kang Min Kim, and co‐workers report a mechanism for the formation of GQDs from MWCNTs by the PLFL process, through the combination of experimental and theoretical studies.

Fundamental Understanding of the Formation Mechanism for Graphene Quantum Dots Fabricated by Pulsed Laser Fragmentation in Liquid: Experimental and Theoretical Insight.

The pulsed laser fragmentation in liquid (PLFL) process is a promising technique for the synthesis of carbon-based functional materials. In particular, there has been considerable attention on graphene quantum dots (GQDs) derived from multiwalled carbon nanotubes (MWCNTs) by the PLFL process, owing to the low cost and rapid processing time involved. However, a fundamental deep understanding of the formation of GQDs from MWCNTs by PLFL has still not been achieved despite the high demand. In this work, a mechanism for the formation of GQDs from MWCNTs by the PLFL process is reported, through the combination of experimental and theoretical studies. Both the experimental and computational results demonstrate that the formation of GQDs strongly depends on the pulse laser energy. Both methods demonstrate that the critical energy point, where a plasma plume is generated on the surface of the MWCNTs, should be precisely maintained to produce GQDs; otherwise, an amorphous carbon structure is favorably formed from the scattered carbons.

ZnO Nanoparticle/Graphene Hybrid Photodetectors via Laser Fragmentation in Liquid.

By combining the enhanced photosensitive properties of zinc oxide nanoparticles and the excellent transport characteristics of graphene, UV-sensitive, solar-blind hybrid optoelectronic devices have been demonstrated. These hybrid devices offer high responsivity and gain, making them well suited for photodetector applications. Here, we report a hybrid ZnO nanoparticle/graphene phototransistor that exhibits a responsivity up to 4 × 104 AW−1 and gain of up to 1.3 × 105 with high UV wavelength selectivity. ZnO nanoparticles were synthesized by pulsed laser fragmentation in liquid to attain a simple, efficient, ligand-free method for nanoparticle fabrication. By combining simple fabrication processes with a promising device architecture, highly sensitive ZnO nanoparticle/graphene UV photodetectors were successfully demonstrated.

Surfactant free stable cobalt oxide nanocolloid in water by pulsed laser fragmentation and its thin films for visible light photocatalysis

Stable, pure nanocolloid of cobalt oxide (Co2O3) in water was prepared by pulsed laser fragmentation in liquid (PLFL) technique. Cobalt oxide powder with black color turned to golden yellow for the nanocolloid after laser fragmentation in water. The structure and morphology of the nanoparticles were analyzed by transmission electron microscopy. Spherical nanoparticles of cobalt oxide (∼10−20 nm) were obtained by PLFL. Nanostructured cobalt oxide thin films were fabricated by spray deposition of the cobalt oxide nanocolloid onto heated glass substrates. Scanning electron microscopy analysis showed that the thin films surfaces were uniform with some porosity, layered nature that had a transformation on thermal treatments. Raman spectroscopic results matched with the peaks for Co2O3 in literature. XPS results of the surface of the films exhibited a difference in oxygen content which was confirmed by XPS mapping. Photocatalytic activities for the as prepared and annealed thin films were studied using methylene blue as a contaminant under irradiation of visible light from a solar simulator. The results showed good visible light photocatalytic activity for the cobalt oxide nanostructured thin films and an enhancement with increase in the annealing temperature as compared to the commercial cobalt oxide powder.

Effect of nanoparticle additivation on the microstructure and microhardness of oxide dispersion strengthened steels produced by laser powder bed fusion and directed energy deposition

In this contribution, the effect of nanoparticle additivation on the microstructure and microhardness of oxide dispersion strengthened steels (ODS) manufactured by laser powder bed fusion (L-PBF) and directed energy deposition (DED) additive manufacturing (AM) is studied. The powder composites are made of micrometer-sized iron-chromium-alloy based powder which are homogenously decorated with Y2O3 nanoparticles synthesized by pulsed laser fragmentation in water. Consolidated by L-PBF and DED, an enhanced microhardness of the AM-built ODS sample is found. This increase is related to the significant microstructural differences found between the differently processed samples.

Laser Fragmentation-Induced Defect-Rich Cobalt Oxide Nanoparticles for Electrochemical Oxygen Evolution Reaction.

Sub‐5 nm cobalt oxide nanoparticles are produced in a flowing water system by pulsed laser fragmentation in liquid (PLFL). Particle fragmentation from 8 nm to 4 nm occurs and is attributed to the oxidation process in water where oxidative species are present and the local temperature is rapidly elevated under laser irradiation. Significantly higher surface area, crystal phase transformation, and formation of structural defects (Co2+ defects and oxygen vacancies) through the PLFL process are evidenced by detailed structural characterizations by nitrogen physisorption, electron microscopy, synchrotron X‐ray diffraction, and X‐ray photoelectron spectroscopy. When employed as electrocatalysts for the oxygen evolution reaction under alkaline conditions, the fragmented cobalt oxides exhibit superior catalytic activity over pristine and nanocast cobalt oxides, delivering a current density of 10 mA cm−2 at 369 mV and a Tafel slope of 46 mV dec−1, which is attributed to a larger exposed active surface area, the formation of defects, and an increased charge transfer rate. The study provides an effective approach to engineering cobalt oxide nanostructures in a flowing water system, which shows great potential for sustainable production of active cobalt catalysts.

Nanoflakes of zinc oxide:cobalt oxide composites by pulsed laser fragmentation for visible light photocatalysis

Metal oxide nanomaterials as visible light photocatalysts are of special interest for the research community. We report synthesis and properties of nanocomposites of zinc oxide with cobalt oxide by cryomilling followed by pulsed laser fragmentation technique for the first time. Structure, morphology, composition, optical properties and visible light photocatalysis of these nanocomposites are investigated. Morphological analysis showed that pulsed laser fragmentation in water resulted with nanoflakes. The optical absorption in visible range was enhanced by addition of cobalt oxide. Chemical states and mapping studies of the sample surfaces showed their uniformity of elemental composition. They were used for photocatalytic studies under visible light from a solar simulator (200 W) using methylene blue dye as the contaminant. These nanocomposites showed good stability and cyclic photocatalytic activity under visible light irradiation. The results show enhanced and cyclic visible light photocatalytic activities of metal oxide nanocomposites designed by pulsed laser fragmentation.

Synergism between Specific Halide Anions and pH Effects during Nanosecond Laser Fragmentation of Ligand-Free Gold Nanoparticles.

Gold nanoclusters (AuNCs) with diameters smaller than 3 nm are an emerging field of research because they possess interesting optical properties, such as photoluminescence. However, to date, it is still difficult to distinguish whether these properties originate from the cores of the nanoparticles or from the adsorbates on their surfaces. Hence, there is a high demand for ligand-free, ultra-small particles because they make it possible to study ligand and core effects separately. Pulsed laser fragmentation in liquids (LFL) is a convenient route for the synthesis of ligand-free AuNCs. The influence of physical parameters, such as melting and evaporation, on the LFL process is well understood both theoretically and experimentally. However, the impact of the chemical composition of the medium during LFL, which critically affects the particle formation process, has been less well examined. Therefore, in this work, we elucidate the extent to which the ionic strength, the pH value, and the nature of the halide anion that is present, that is, F-, Cl-, Br-, or I-, influence the particle size distribution of the LFL product and the mean yield of small particles (<3 nm) of the product. We showed that the yield of small particles can be enhanced by the synergism between pH and specific ion effects, which probably is attributable to the adsorption of specific anions. In addition, our findings indicated that anion-based stabilization depends critically on the type of anion. A direct Hofmeister effect was observed for anions in the neutral pH regime, whereas an indirect Hofmeister series was reported in alkaline solution, which probably was due to the more hydrophilic surfaces of the AuNCs that were formed.

Laser Fragmentation of Colloidal Gold Nanoparticles with High-Intensity Nanosecond Pulses is Driven by a Single-Step Fragmentation Mechanism with a Defined Educt Particle-Size Threshold

Laser-inducd fragmentation is a promising tool for controlling the particle size of ligand-free colloidal nanoparticles and to synthesize ligand-free gold nanoclusters. However, because the underlying mechanisms are not fully understood, increasing the yield of this process remains challenging. In this work, we examine the pulsed laser fragmentation of gold nanoparticles in liquid under statistical single-pulse conditions with high-fluence nanosecond pulses and correlate them with the educt particle size, number of pulses, and laser fluence. We conclusively prove that the fragmentation process of gold nanoparticles is a one-pulse and one-step event, which yields monomodal particles of ≪10 nm down to 2.8 +/- 0.1 nm when exceeding a pulse peak power of 1.6 × 1012 W/m2 and when all educt particles are larger than 13.4 nm. This size threshold for quantitative fragmentation fits well with the size limit of 13.1 nm calculated with respect to the evaporation–heat–energy balance. Furthermore, we found strong evid...

Corrigendum to “Quantification of mass-specific laser energy input converted into particle properties during picosecond pulsed laser fragmentation of zinc oxide and boron carbide in liquids” [Appl. Surf. Sci. 348 (September) (2015) 22–29

Corrigendum to “Quantification of mass-specific laser energy input converted into particle properties during picosecond pulsed laser fragmentation of zinc oxide and boron carbide in liquids” [Appl. Surf. Sci. 348 (September) (2015) 22–29