Ilya V. Baimler
Alexander V. Simakin
Alexey S. Dorokhov2
Sergey V. Gudkov- 1Prokhorov General Physics Institute of the Russian Academy of Sciences, Moscow, Russia
- 2Federal State Budgetary Scientific Institution “Federal Scientific Agroengineering Center VIM” 5 (FSAC VIM), Moscow, Russia
- 3Institute of Biology and Biomedicine, Lobachevsky State University of Nizhny Novgorod, Moscow, Russia
The development of various nanomaterials production technologies has led to the possibility of producing nanoparticles (NPs) and nanostructures, which can find a wide range of applications, from the fabrication of microelectronic devices to the improvement of material properties and the treatment of cancer. The unique characteristics of nanoparticles are primarily due to their small size, which makes size control important in their preparation. Modification of nanoparticles by laser irradiation and obtaining desired nanoparticle properties is a promising approach because of its ease of implementation. The purpose of this review is to analyze the works devoted to the study of laser-induced heating and melting of nanoparticles, to collect information and evaluate the results of using this method for functionalization and modification of metallic nanoparticles, and to discuss promising directions for the use of this technique.
1 Introduction
Nowadays, nanoparticles play a key role in science and are widely used in various fields of industry (Alsaba et al., 2020), agro-technology (Kaningini et al., 2022; Gudkov et al., 2024), biochemistry (Rico et al., 2015), biophysics (Moore and Chow, 2021) and catalysis (Tack et al., 2024). Synthesis and modification of nanoparticles by laser irradiation is a well-known method for fabrication of nanoparticles with high purity surface in liquids using laser pulses, which has proven to be an environmentally friendly, simple and convenient method for obtaining nanoscale objects (AlMalki et al., 2022; Jiang et al., 2022; Bhardwaj et al., 2020).
Due to their unique optical properties, nanoparticles are well suited for heating by laser radiation (Qin and Bischof, 2012). In this context, colloidal particles are of particular interest, since conventional heating methods limit the maximum achievable temperature to the boiling point of the solvent. Colloidal particle solutions modified by laser heating and melting can potentially be used in various fields of nanotechnology, ranging from biological imaging (Saha et al., 2012), drug delivery (Wilczewska et al., 2012), water purification (Kefeni et al., 2017) to the generation of high-frequency mechanical vibrations (Pelton et al., 2009).
The heating of metallic nanoparticles is based on the absorption of light by the nanoparticles and it occurs in the following way: free electrons absorb photon energy within a time scale of 100 femtoseconds (Heilweil and Hochstrasser, 1985; Ekici et al., 2008). After that, the equilibrium state is reached through electron-electron relaxation within 10–100 femtoseconds (Heilweil and Hochstrasser, 1985; Hodak et al., 1998). Due to the electron-phonon interaction that occurs between 100 femtoseconds and picoseconds, the temperature of the particle increases (Letfullin et al., 2008). Finally, the increase in temperature in the surrounding environment occurs due to energy transfer between the particles and the surrounding medium through phonon-phonon interactions that take place over a range from picoseconds to nanoseconds (Ekici et al., 2008). It has been shown that certain parameters, such as laser fluence (Pustovalov et al., 2008; Nedyalkov et al., 2011), pulse duration (Pustovalov, 2006), wavelength (Astafyeva et al., 2017), repetition rates (Sobhan et al., 2010), as well as nanoparticle size (Duan et al., 2018) and material (Pyatenko et al., 2013) affect the threshold values for the onset of melting of nanoparticles and their heating rates.
Melting is a well-known and well-studied phenomenon that continues to reveal new aspects when it occurs under laser irradiation of nano-objects (Nanda, 2009). Recent experimental data on the anomalously slow nanosecond melting process of thin gold films under the influence of femtosecond laser pulses have prompted studies aimed at understanding the mechanisms underlying this phenomenon (Arefev et al., 2022).
The key parameter when considering the processes of particle heating under laser irradiation is the amount of heat loss from nanoparticles to the surrounding solvent due to conduction, convection, and radiation heat transfer (Wang et al., 2012). It has recently been shown that heat transfer to the surrounding particle environment is not solely determined by the thermal conductivity of the surrounding fluid. Particle cooling occurs by heat transfer through the vapor/liquid interface (Plech et al., 2004). In this case, the characteristic length of thermodiffusion can play a crucial role in the formation of nanoparticles and bulk materials using laser pulses (Llamosa et al., 2013).
When a nanoparticle is exposed to excessively intense laser irradiation, the energy of which exceeds the melting and ionization energies, it passes into the state of nanoplasma, which is located in a shell of liquid vaporized during heating, which is accompanied by a number of nonequilibrium dynamical processes (Niozu et al., 2021). It is worth noting that ionization mechanisms, as studies show, depend on the pulse duration - multiphoton photoionization is characteristic of femtosecond pulses, and avalanche ionization is characteristic of pico- and nanosecond pulses (Noack and Vogel, 1999; Linz et al., 2016; Yang et al., 2023). The formation of a thermally induced vapor-gas shell around the particle plays one of the key roles in the processes of changing the morphology and size of the particle (Metwally et al., 2015; Lombard et al., 2014).
At present, the mechanisms of heat transfer between nanoparticles and liquids in the context of nanoparticle wetting phenomena are poorly understood (Tascini et al., 2017). Unwanted thermal effects are another problem (Hashemi et al., 2019). In order to prevent unwanted heating, it is necessary to investigate the localized heating effect of particles. The peculiarity of the study of this problem lies in the difficulty of determining temperatures, since the accurate determination of temperature in the nanoscale region has a number of peculiarities (Liu and Liu, 2019).
A promising area of research in nanomedicine involves the use of nanoparticles that can accumulate in disease foci for drug delivery or thermal destruction of cells. Nanoparticles entering diseased tissues are activated by laser radiation, which initiates heat transfer by the particle and changes the temperatures of the medium (Riley and Day, 2017; Day et al., 2009). It is assumed that heat can be controlled and focused at the nanoscale, which allows precise control of the processes that occur (Terentyuk et al., 2009; Sokolovskaya et al., 2021).
The processes of particle heating by laser radiation are also involved in such technologies as selective laser melting (SLM) (Liu et al., 2011), laser sintering, creation of hybrid materials and alloys (Xiao et al., 2020). Laser-induced heating is widely used to modify and form nanostructures on metal surfaces (Kucherik et al., 2021; Zhu et al., 2016; Yadavali et al., 2016; Sdvizhenskii and Lednev, 2022). All the techniques related to the heating and melting of nanoparticles under the influence of laser radiation, which will be discussed in this review, are presented in Figure 1A.
Figure 1. (A) Schematic representation of the application of laser heating of nanoparticles; (B) Dependence of size of Au nanoparticles upon laser-induced irradiation of colloids during laser fragmentation in aqueous solutions depending on laser fluence, pulse duration, irradiation time and wavelength; (C) A schematic representation of the synthesis process for nanocomposite materials through laser irradiation of nanoparticle colloids in a liquid medium; (D) Scheme of the basic process using laser sintering of nanoparticles; (E) Diagram of possible applications for the nanoparticle-enhanced materials.
One of the most popular nanoparticle materials used in nanotechnology is gold. Gold nanoparticles possessing surface plasmon resonance are currently used as promising heating centers in various chemical and medical applications (Qin and Bischof, 2012; Gorin et al., 2008; Yang et al., 2019). However, the suitable wavelength for heating nanoparticles, i.e., the surface plasmon resonance wavelength, is only in the visible spectrum, and the maximum achievable temperature is limited by their relatively low melting point. The use of other materials as potential heating centers for nanoparticles will circumvent these problems.
This review discusses the current state of knowledge on the technology of laser-induced melting of metal nanoparticles. The advantages and potential problems of this technology, current applications, and promising directions for further development are discussed.
2 Control of the sizes and morphology of nanoparticles during the heating process
Controlling the shape of nanoparticles is an important aspect to adjust the parameters of nanoparticle technologies. For example, the shape of the particles can influence the signal of nanoparticle-enhanced laser breakdown spectroscopy (NELIBS). Experimental results show that silver nanowires and nanocubes enhance LIBS signals compared to spherical particles (Abdelhamid et al., 2020). The irradiation of colloids by laser irradiation can reduce the size of nanoparticles and decrease the width of the size distribution. The final particle size and distribution width can be controlled by varying the irradiation intensity (Mafuné et al., 2001). The application of laser pulse fragmentation in liquid (LFL) method can produce stable colloidal gold nanoparticles in water (Ashikkalieva et al., 2022). The final size of fragmented nanoparticles is mainly determined by the exposure time and radiation intensity (Vasa et al., 2014). Coating plasmonic nanoparticles with temperature-sensitive polymers allows tracking the temperature increase during laser heating by monitoring the shift of the plasmon resonance peak and absorption spectrum, which are affected by the temperature-dependent refractive index of the medium (Honda et al., 2011; Mikami et al., 2021).
The technology of laser-induced heating also makes it possible to change the morphology of nanoparticles. It was found that irradiation of ellipsoidal gold nanoparticles results in their transition to spherical shape at temperatures much lower than their melting temperature. The effect of particle shape change may be due to partial surface melting (Inasawa et al., 2005). A method of producing spherical porous gold nanoparticles on glass substrates using ultraviolet laser followed by chemical selective etching is reported. This method allows the creation of branched nanometer-scale structures inside spherical particles (Schmidl et al., 2022).
The choice of the required laser intensity and wavelength allows selectively obtaining particles of the desired shape - spheres, nanorods, nanoprisms, one-dimensional structures, nanochains, etc. By adjusting the wavelength of radiation, it is possible to choose the spatial extent of the ensembles of heated nanoparticles, which allows controlling the morphology of nanostructures formed during melting (Tarasenko et al., 2005; Catone et al., 2018; Ashikkalieva et al., 2023). Laser size reduction and formation of nanostructures from gold nanoparticles is a promising method for producing nanoscale devices containing nanoparticles and nanowires of desired sizes (Mafuné et al., 2003; Simakin et al., 2021; Kirichenko et al., 2012; Serkov et al., 2015a; Serkov et al., 2015b).
An important factor in particle heating is the duration of the radiation pulse. The use of nanosecond pulses leads to either fragmentation or complete melting of the material and the formation of spherical-shaped particles, while energetically the melting threshold was higher by two orders of magnitude compared to femtosecond pulses (Link et al., 2000a). Irradiation of gold nanoparticles with picosecond pulses of gold nanoparticles at a wavelength of 532 nm shows lower heating efficiency compared to other wavelengths (Plech et al., 2022). It is suggested that the decrease in heating efficiency can be attributed to the effects of scattering enhancement, thermoelectronic emission, plasma formation, plasmon interaction with the surroundings and the effects of partial lattice melting and deformation. It was found that femtosecond laser pulses are more suitable for the photothermal formation of gold nanorods, since the energy transfer to the crystal lattice occurs faster than the characteristic electron-phonon relaxation time (Link et al., 2000a).
Plasmonic nanoparticles can be effectively heated when exposed to femtosecond laser pulses with very low energy densities (Huang et al., 2015). It is shown that the efficiency of particle heating under these conditions depends on the local geometry of each nanoparticle and the polarization of the incident laser radiation.
In some cases, laser-induced heating of particles allows the material of nanoparticles to be transferred to other phase states. For example, when colloidal dispersions of copper oxide nanoparticles were irradiated with nanosecond radiation with a wavelength of 532 nm, phase transitions from copper (II) oxide to crystalline copper were observed in nanoparticles. The phase transition was limited to the minimum particle size (23–29 nm), due to more efficient heating process, less cooling effect (Kranz et al., 2022). X-ray diffraction study of MnO nanoparticle samples showed that laser heating led to changes in the existing phases of the sample, including the destruction of the MnO phase and the formation of new phases such as MnO2, Mn3O4, and MnOOH, as well as the deposition of Mn2+ ions on the sample surface (Hadžić et al., 2018). Laser heating and fragmentation of selenium nanoparticles leads to the formation of crystalline selenium in new phases (Varlamova et al., 2023; Baimler et al., 2024; Singh et al., 2010; Poborchii et al., 1999; Sakaguchi and Tamura, 2021).
The potential of submicron spherical boron carbide-based B4C boron carbide particles as nanoscale heating agents is currently being investigated because B4C has a broader optical absorption spectrum and a higher melting point than gold (Pavlov et al., 2022; Aiyyzhy et al., 2022a; Mayelifartash et al., 2021; Stone et al., 2024). The experiment demonstrated that B4C particles exhibit a significant response in the wavelength range of 300–1,100 nm and are capable of acting as a nanoscale heater at temperatures exceeding 2000 K, which can be utilized in the design of volume-selective heating agents (Kojima et al., 2020).
During heating and melting of nanoparticles, the formation of larger particles formed by the fusion of several molten particles is sometimes observed. A key role in the formation of large submicron particles is played by the vapor-gas shell surrounding the particles during heating and boiling of the surrounding liquid (Tabayashi et al., 2021). It was found that the use of high pressures in laser irradiation of colloids leads to a decrease in the size of nanoparticles, which is associated with the processes of gas bubble formation and changes in the dynamics of heat loss in heated particles (Werner and Hashimoto, 2013; Wei and Saitow, 2012). Wettability affects the thermal conductivity of the nanoparticle-water interface. Greater wettability enhances the interaction of low-frequency phonon modes at the solid-liquid interface, thereby increasing the efficiency of thermal energy transfer, as has been shown for Fe particles (Ma et al., 2024a). The thermal effect was found to be the main reason for the transformation of the atomic structure of single-crystal gold nanoparticles. Nanoparticles with defects in the crystal structure show increased surface activity due to low coordination number (Zhu et al., 2021).
The process of laser heating of nanoparticles is studied using analytical methods and modeling. A significant part of the recently published review (Pustovalov, 2024) is devoted to modeling of the processes of heating by laser radiation of individual particles and their aggregates.
The study of diffraction profiles of nanoparticles and their atomistic modeling during their laser fragmentation by picosecond laser radiation allowed to identify the main stages of the process of nanoparticle heating and fragmentation. At low laser intensity, a short-term overheating of crystalline nanoparticles above the melting temperature, melting, subsequent cooling and solidification are observed. When the radiation energy density is three times the melting threshold, fragmentation begins with the evaporation of gold atoms and their subsequent condensation into small nanoparticles. When the energy density increases to more than five times the melting threshold, there is a transition to rapid (explosive) phase destruction of superheated nanoparticles into small liquid droplets and vaporized atoms (Plech et al., 2023). Atomistic modeling also shows that the combination of lattice superheating and laser-induced stress relaxation ensures the predominance of the homogeneous melting process at all energy levels below the melting threshold, keeping the melting duration at approximately 100 picoseconds or less (Arefev et al., 2022).
The cluster-based molecular dynamics of the two-temperature model becomes an effective method to study the microscopic dynamics of nanoparticles. The two-temperature model, integrated with the molecular dynamics model and the localized melting model, effectively simulates the energy transfer and relaxation processes that underlie the final size and morphology of nanoparticles (Chen et al., 2014; Cui et al., 2013; Alavi and Thompson, 2006; Shibuta and Suzuki, 2007).
The results of laser-induced irradiation of nanoparticle colloids in water are given in Table 1.
Table 1. List of experimental works on synthesis, structuring and modification of nanoparticles using laser-induced irradiation.
Analysis of the results of experimental work on laser irradiation and laser fragmentation of gold colloids in water shows that the main parameters determining the particle size are fluence, pulse duration, pulse repetition rate and irradiation duration (Figure 1B). Changes in fluence can lead to changes in the shape of gold particles (0.001–0.01 J/cm2), their melting and aggregation into larger particles (0.1 J/cm2), and fragmentation and formation of smaller particles (1–100 J/cm2). The use of femtosecond pulses demonstrates the possibility of obtaining particles in a wider range of sizes compared to pico- and nanosecond pulses. Increasing the irradiation time and radiation frequency increases the number of interactions of laser pulses with particles, which leads to a decrease in size. Irradiation of colloids at a wavelength coinciding with the Au plasmon resonance wavelength leads to more efficient melting and formation of large aggregates.
3 The formation of nanostructured alloys and hybrid materials through laser melting of nanoparticles
Significant interest is emerging in the development of alloy metallic nanoparticles, due to their synergistic effect and because of their unique hybrid characteristics. Alloy nanoparticles are known to have higher catalytic activity than their monometallic counterparts (Xing et al., 2023; Khan et al., 2020; Jiang et al., 2023). Current research is focused on the creation of metal oxide nanostructures based on CuO, ZnO, TiO₂ and Fe₂O₃ (Pembere et al., 2022; Mintcheva et al., 2020; Nag et al., 2023; Omelchenko et al., 2015). Irradiation of a mixture of nanoparticle colloids of different materials allows the preparation of new nanocomposite materials (Golubovskaya et al., 2024; Fakhrutdinova et al., 2024). For example, irradiation of a mixture of colloids of two different nanoparticle plasmonic materials of gold and silver with femtosecond pulses allows to obtain Au-Ag nanocomposites, the formation of which involved the mechanism of laser melting and doping (Hidayah and Herbani, 2020). The formation of Au/MxOy (M = Fe, Co, Ni) composite nanoparticles with different morphology and sizes was observed by laser irradiation of particle colloids during their mixing (Swiatkowska-Warkocka et al., 2017). A schematic representation of the process of creating hybrid/alloy nanomaterials is shown in Figure 1C. It is possible to form alloy nanoparticles and hybrid materials by laser-induced irradiation of double thin films of metals using laser radiation. For example (Dzienny et al., 2022), describes a method for producing Au-Sn particles by laser-induced dewetting. In Kovalev et al. (2023) the technology of hyperdoping of silicon films with gold by irradiation of Au and Si double films with nano- and picosecond radiation is reported. In Hodges et al. (2017), a technique for synthesizing three-component Ag-Pt-Fe3O4 and Au-Pt-Fe3O4 heterotrimers is described. In Amendola et al. (2017) it is reported about obtaining Au-Fe alloy composite nanoparticles by laser ablation of multilayer gold and iron films of different thickness in ethanol and water. In some cases, the formation of alloy particles occurred at room temperature by simple mixing of colloids, as shown in Křenek et al. (2022), where TiSi2 nanoparticles were obtained.
4 Laser sintering of metal nanoparticles
Laser sintering has been a well-established method for several years and is widely used with continuous and pulsed lasers of various durations. This technology is widely used in the production of electronics devices. The characteristics of devices fabricated by this method depend to a large extent on the sintering conditions, melt state, laser radiation parameters, particle structure and substrate condition (Chen et al., 2023). A schematic representation of the basic laser sintering process is shown in Figure 1D. Using the low-temperature sintering method, stable Cu@Ag nanoparticles in the form of nanoribbons were synthesized, which may have practical applications in flexible printed electronics (Zhang et al., 2022). Laser sintering has been reported to produce ruby particles by irradiating Al2O3 and Cr2O3 powders in quasi-continuous mode (Aiyyzhy et al., 2023). The ruby particles obtained by the authors were then used in the manufacture of photoconversion coatings for greenhouses (Paskhin et al., 2023).
Laser-induced forward transfer (LIFT) and selective laser sintering (SLS) are two promising technologies based on the process of laser heating of materials that can be used to create a conductive layer of metallic nanoparticle ink on various substrates (Lim et al., 2020).
Selective laser melting (SLM) is a laser additive manufacturing technique based on the principle of layer-by-layer material deposition. SLM is used to fabricate various materials including alloys of different metals (Lu and Zhuo, 2023; Lu et al., 2023; Ma et al., 2024b; Sajjadi et al., 2024) and composite materials (Xi et al., 2021; Erutin et al., 2023).
Despite the extensive literature on conventional laser sintering methods, the use of ultra-short femtosecond pulses in this technology remains a relatively unexplored area (Sharif et al., 2022).
5 Nanoparticle enhanced thermal properties of materials
Incorporation of nanoparticles into various materials demonstrates significant changes in the thermal properties of the starting material. A new class of substances, nanofluids, have recently become the object of close attention due to a number of unique properties. Nanofluids are a mixture of nanoparticles and a solvent (Das et al., 2006). Nanofluids have been shown to significantly improve the thermal properties of basic solvents (Kumar et al., 2018). The improvement in the heat transfer properties of nanofluids has led to interest in their study and use in various engineering applications. These include nuclear technology (Buongiorno et al., 2008), desalination (Iqbal et al., 2021), machining (Ramesh and Prabhu, 2011), and cooling (Rafati et al., 2012). They are also used in solar energy (Izadi and Assad, 2024) and electron cooling (Moita et al., 2021).
Another promising class of materials, phase-change materials (PCM), can be used for heat storage and transfer (Chen et al., 2020). The addition of nanoparticles to these materials (NPCM) has been demonstrated to increase the thermal conductivity of the material (Khodadadi et al., 2013; Colla et al., 2017; Krishna et al., 2017) and change the phase transition temperatures (Lin and Al-Kayiem, 2016; Munyalo and Zhang, 2018). Laser heating and the addition of nanoparticles to PCMs will allow for a faster transition of the material into the crystalline phase (Kozyukhin et al., 2019). A diagram illustrating possible applications of the materials described is presented in Figure 1E.
In perspective, nanoparticles could be used to alter the properties of a wider range of materials. It has been shown that the volume of the melt region and the size of the heat affected zone during the melting and solidification processes of materials can be controlled by adding aluminum and silicon carbide nanoparticles to the material (Ma et al., 2017).
6 Conclusion
This mini-review provides a brief overview of recent advances in research and technology based on the heating and melting of nanoscale particles under the action of laser radiation. Nanoparticles themselves are of great interest for study and use in various fields ranging from medicine, agricultural engineering, catalysis to the creation of electronic devices. Moreover, with the help of laser radiation it is quite easy to change the key characteristics of nanoparticles (shape and size), to create new materials based on particles, to change the thermal characteristics of materials thereby expanding the possibilities of nanomaterials application. Overall, promising areas for research in this field will include the study of the interactions between nanoparticles and femtosecond laser pulses. Additionally, there is an interest in using these pulses to create novel hybrid materials such as nanocomposites and nanoparticles-based alloys through the use of the effect of localized surface melting of nanoparticles. Furthermore, the development of new classes of nanoparticle-enhanced materials, such as nanofluids and NPCM, has increased interest in understanding the impact of nanoparticles on macroscopic properties of the materials.
Author contributions
IB: Conceptualization, Writing–original draft. AS: Conceptualization, Writing–review and editing. AD: Conceptualization, Writing–review and editing. SG: Conceptualization, Writing–review and editing.
Funding
The author(s) declare that financial support was received for the research, authorship, and/or publication of this article. This work was supported by the Ministry of Science and Education of the Russian Federation (Grant Agreement 075-15-2024-540).
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Publisher’s note
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.
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Keywords: nanoparticles, laser radiation, laser fragmentation, laser heating, laser melting
Citation: Baimler IV, Simakin AV, Dorokhov AS and Gudkov SV (2024) Mini-review on laser-induced nanoparticle heating and melting. Front. Chem. 12:1463612. doi: 10.3389/fchem.2024.1463612
Received: 12 July 2024; Accepted: 28 October 2024;
Published: 06 November 2024.
Edited by:
Satyabrata Mohapatra, Guru Gobind Singh Indraprastha University, IndiaReviewed by:
Gopala Krishna Podagatlapalli, Gandhi Institute of Technology and Management (GITAM), IndiaZixin Wang, Los Alamos National Laboratory (DOE), United States
Copyright © 2024 Baimler, Simakin, Dorokhov and Gudkov. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
*Correspondence: Ilya V. Baimler, aWx5YWJheW1sZXJAeWFuZGV4LnJ1