Latent ion tracks were finally observed in diamond.

Injecting high-energy heavy ions in the electronic stopping regime into solids can create cylindrical damage zones called latent ion tracks. Although these tracks form in many materials, none have ever been observed in diamond, even when irradiated with high-energy GeV uranium ions. Here we report the first observation of ion track formation in diamond irradiated with 2-9 MeV C60 fullerene ions. Depending on the ion energy, the mean track length (diameter) changed from 17 (3.2) nm to 52 (7.1) nm. High resolution scanning transmission electron microscopy (HR-STEM) indicated the amorphization in the tracks, in which π-bonding signal from graphite was detected by the electron energy loss spectroscopy (EELS). Since the melting transition is not induced in diamond at atmospheric pressure, conventional inelastic thermal spike calculations cannot be applied. Two-temperature molecular dynamics simulations succeeded in the reproduction of both the track formation under MeV C60 irradiations and the no-track formation under GeV monoatomic ion irradiations.

Ion tracks in silicon formed by much lower energy deposition than the track formation threshold.

Damaged regions of cylindrical shapes called ion tracks, typically in nano-meters wide and tens micro-meters long, are formed along the ion trajectories in many insulators, when high energy ions in the electronic stopping regime are injected. In most cases, the ion tracks were assumed as consequences of dense electronic energy deposition from the high energy ions, except some cases where the synergy effect with the nuclear energy deposition plays an important role. In crystalline Si (c-Si), no tracks have been observed with any monomer ions up to GeV. Tracks are formed in c-Si under 40 MeV fullerene (C60) cluster ion irradiation, which provides much higher energy deposition than monomer ions. The track diameter decreases with decreasing the ion energy until they disappear at an extrapolated value of ~ 17 MeV. However, here we report the track formation of 10 nm in diameter under C60 ion irradiation of 6 MeV, i.e., much lower than the extrapolated threshold. The diameters of 10 nm were comparable to those under 40 MeV C60 irradiation. Furthermore, the tracks formed by 6 MeV C60 irradiation consisted of damaged crystalline, while those formed by 40 MeV C60 irradiation were amorphous. The track formation was observed down to 1 MeV and probably lower with decreasing the track diameters. The track lengths were much shorter than those expected from the drop of Se below the threshold. These track formations at such low energies cannot be explained by the conventional purely electronic energy deposition mechanism, indicating another origin, e.g., the synergy effect between the electronic and nuclear energy depositions, or dual transitions of transient melting and boiling.

Matrix-material dependence on the elongation of embedded gold nanoparticles induced by 4 MeV C60 and 200 MeV Xe ion irradiation.

We report the elongation of embedded Au nanoparticles (NPs) in three different matrices, i.e. amorphous carbon (a-C), crystalline indium tin oxide (InxSn1-xOz; ITO) and crystalline calcium fluoride (CaF2), under irradiations of 4 MeV C60 + cluster ions and 200 MeV Xe14+ ions. Under 4 MeV C60 cluster irradiation, strong sputtering is induced in CaF2 layer so that the whole the layer was completely lost at a fluence of 5 × 1013 ions cm-2. Au NPs were partly observed in the SiO2, probably due to the recoil implantation. Amorphous carbon (a-C) layer exhibits low sputtering loss even under 4 MeV C60 irradiation. However, the elongation in a-C layer was low. While the ITO layer showed a certain decrease in thickness under 4 MeV C60 irradiation, large elongation of Au NPs was observed under both 4 MeV C60 and 200 MeV Xe irradiation. The ITO layer preserved the crystallinity even after large elongation was induced. This is the first report of the elongation of metal NPs in a crystalline matrix.

C60 ions of 1 MeV are slow but elongate nanoparticles like swift heavy ions of hundreds MeV.

This study reports that high fluence fullerene ion (C60+) irradiation of 1-6 MeV, which was made possible by a new-type of high-flux ion source, elongates metal nanoparticles (NPs) in amorphous SiO2 as efficiently as swift heavy ions (SHIs) of 200 MeV Xe14+, i.e., two orders of the magnitude higher energy ions. Comparing the irradiation effects induced by both the beams, the stopping processes of C60 ions in SiO2 are discussed in this paper. Despite of having almost the same elongation efficiency, the C60+ irradiation induced ~10 times more efficient sputtering due to the clustering enhancement and/or the synergy effect. Ion tracks of ~10.4 nm in diameter and 60-80 nm in length were observed in crystalline SiO2 under 4 MeV C60 irradiation. While the track diameter was comparable to those by SHIs of the same electronic stopping, much shorter track lengths than those predicted by a rigid C60 molecule model indicates that the fragmentation occurred due to nuclear collisions. The elongation of the metal NPs was induced only down to the depth where the tracks were observed but not beyond.

Plasmonic nanoparticles embedded in single crystals synthesized by gold ion implantation for enhanced optical nonlinearity and efficient Q-switched lasing.

We report on the synthesis of embedded gold (Au) nanoparticles (NPs) in Nd:YAG single crystals using ion implantation and subsequent thermal annealing. Both linear and nonlinear absorption of the Nd:YAG crystals have been enhanced significantly due to the embedded Au NPs, which is induced by the surface plasmon resonance (SPR) effect in the visible light wavelength band. Particularly, through a typical Z-scan system excited by a femtosecond laser at 515 nm within the SPR band, the nonlinear absorption coefficients of crystals with Au NPs have been observed to be nearly 5 orders of magnitude larger than that without Au NPs. This giant enhancement of nonlinear absorption properties is correlated with the saturable absorption (SA) effect, which is the basis of passive Q-switching or mode-locking for pulsed laser generation. In addition, the linear and nonlinear absorption enhancement could be tailored by varying the fluence of implanted Au+ ions, corresponding to the NP size and concentration modulation. Finally, the Nd:YAG wafer with embedded Au NPs has been applied as a saturable absorber in a Pr:LuLiF4 crystal laser cavity, and efficient pulsed laser generation at 639 nm has been realized, which presents superior performance to the MoS2 saturable absorber based system. This work opens an avenue to enhance and modulate the nonlinearities of dielectrics by embedding plasmonic Au NPs for efficient pulsed laser operation.

Are the triple surface plasmon resonances in Zn nanoparticles true?

It has been experimentally and numerically confirmed that zinc (Zn) nanoparticles (NPs) dispersed in silica exhibit two optical extinction peaks around ∼250 nm (1st peak) and ∼1050 nm (2nd peak), both of which were ascribed to surface plasmon resonances (SPRs) in the broad sense, i.e., the dual SPRs. Recently, Kuiri and Majhi (KM) observed the 3rd peak around ∼900 nm by calculations, and proposed the triple SPRs for Zn NPs without any experimental confirmation. This paper claims that the 3rd peak has never been observed in any experiments nor in any calculations except given by KM. They justified the triple resonances from an approximated SPR criterion, ε 1Zn(ω) + 2ε 1SiO2 (ω) = 0, which is not valid for non-idealized metals like Zn, because the imaginary part of the dielectric function ε 2Zn(ω) is not negligible. Instead, a rigorous SPR criterion predicts the dual resonances only. From comparisons with ab initio band calculations, the 1st and 2nd extinction peak are ascribed to resonantly enhanced inter-band transitions (so-called electronic resonance) and intra-band transitions (SPR in the narrow sense), respectively. Since either of the peaks arises from the resonant enhancement due to the dielectric function, both the peaks are regarded as SPRs in the broad sense, i.e. the dual SPRs.

Shape elongation of Zn nanoparticles in silica irradiated with swift heavy ions of different species and energies: scaling law and some insights on the elongation mechanism.

Zinc nanoparticles (NPs) embedded in silica were irradiated with swift heavy ions (SHIs) of seven different combinations of species and energies. The shape elongation induced by the irradiations was evaluated by optical linear dichroism (OLD) spectroscopy, which is a sensitive tool for determining the change in the mean aspect ratio (AR) of NPs. Although the mean AR change indicated a linear fluence dependence in the low- and medium-fluence regions, it indicated a nonlinear dependence in the high-fluence region. The data reveal that the elongation efficiency of Zn is correlated with the electronic stopping power 'Se in silica' and is not correlated with either the 'Se in Zn' or the nuclear stopping power. The elongation efficiency plotted as a function of the 'Se in silica' revealed a linear relationship, with a threshold value of ∼2 keV nm(-1), which is the same dependence exhibited by the ion-track formation in silica. The log-log plot showed that the elongation efficiency increased linearly with Se above a critical value of ∼3 keV nm(-1) and steeply decreased with Se to the power of 5 below the critical Se. The steep decrease can be ascribed to the discontinuous nature of the ion tracks, which is expected at Se ∼ 2-4 keV nm(-1) in silica. The fluence Φ dependences of AR - 1 under various irradiations are well-normalized with the electronic energy deposition of SHIs, i.e., the product of Se and Φ, with a Se greater than the same critical value of ∼3 keV nm(-1). The normalized data above the critical value fell on a linear relation, AR(Φ) - 1 ∝ SeΦ, for SeΦ < 2 keV nm(-3) and a sublinear relation, AR(Φ) - 1 ∝ (SeΦ)(1/2) for SeΦ > 2 keV nm(-3). On the basis of these experimental results, we discuss some insights into the elongation mechanism.

Synthesis of embedded Au nanostructures by ion irradiation: influence of ion induced viscous flow and sputtering.

The ion-irradiation induced synthesis of embedded Au nanoparticles (NPs) into glass from islands of Au on a glass substrate is studied in the context of recoiling atoms, sputtering and viscous flow. Cross sectional transmission electron microscopy studies revealed the formation of Au NPs embedded in the glass substrates by the 50 keV Si(-) ion irradiation of irregularly shaped Au nanostructures on the glass surfaces at a fluence of 3 × 10(16) ions/cm(2). The depth profiles of Au in the samples were obtained from high-resolution Rutherford backscattering spectrometry studies. The results from TRIDYN simulation reveal the role of various ion-induced processes during the synthesis of the embedded Au NPs, viz. sputtering and recoiling atoms. Simulation and experimental results suggest that the viscous flow is one of the major factors that are responsible for the embedding of Au nanoparticles into the glass substrate.

Optical birefringence of Zn nanoparticles embedded in silica induced by swift heavy-ion irradiation.

Zn nanoparticles (NPs) embedded in a silica matrix subjected to irradiation with swift heavy ions of 200 MeV Xe¹4⁺ have been found to undergo shape elongation from spheres to prolate-spheroids while maintaining the major axes of the NPs in parallel alignment. The directionally-aligned Zn spheroids enable acquisition of optical properties, such as linear dichroism and birefringence. In this paper, the birefringence of the Zn spheroids was evaluated by the crossed-Nicols (XN) transmittance, where a sample was inserted between a pair of optical polarizers that were set in an orthogonal configuration. Linearly-polarized light aligned by the first polarizer was transformed to an elliptic polarization by the birefringence of the Zn spheroids. The existence of the birefringence was confirmed by the non-zero transmittance of the second polarizer in the orthogonal configuration. The sample irradiated with a fluence of 5.0 × 10¹³ ions/cm² exhibited a maximum XN transmittance of 2.1% at a photon energy of ~4 eV. The XN transmission was observed down to a fluence of 1.0 × 10¹² ions/cm², but reduced below the detection limit at a fluence of 1.0 × 10¹¹ ions/cm². The possible application of the elongated Zn NPs as a polarizer with nanometric thickness working in the near- and mid-ultraviolet region is discussed.

Role of thermodynamics in the shape transformation of embedded metal nanoparticles induced by swift heavy-ion irradiation.

Swift heavy-ion irradiation of elemental metal nanoparticles (NPs) embedded in amorphous SiO(2) induces a spherical to rodlike shape transformation with the direction of NP elongation aligned to that of the incident ion. Large, once-spherical NPs become progressively more rodlike while small NPs below a critical diameter do not elongate but dissolve in the matrix. We examine this shape transformation for ten metals under a common irradiation condition to achieve mechanistic insight into the transformation process. Subtle differences are apparent including the saturation of the elongated NP width at a minimum sustainable, metal-specific value. Elongated NPs of lesser width are unstable and subject to vaporization. Furthermore, we demonstrate the elongation process is governed by the formation of a molten ion-track in amorphous SiO(2) such that upon saturation the elongated NP width never exceeds the molten ion-track diameter.

Microstrip structures of ZnO nanoparticle aggregates of millimetric length formed by selected-area ion implantation and thermal oxidation.

Regularly arrayed microstrip regions of width approximately 1.4 microm and length extending up to approximately 5 mm, consisting of ZnO nanoparticles (NPs) of diameter approximately 50 nm, were fabricated on silica substrates by a two-step process: i.e., selected-area ion implantation and thermal oxidation. The implantation of 60 keV Zn ions in periodic microstrip regions via a resist mask generated periodic grooves with large wings on the surface of silica glass, which can be ascribed to the radiation-induced plastic deformation of silica and sputtering loss. This is the lowest record of the electronic energy loss (S(e)) value to induce the radiation-induced plastic deformation of silica, while no or very low threshold energy has been predicted from a recent study. After thermal oxidation at 700 degrees C for 1 h, the groove structures with the wings disappeared, and periodic microstrips of ZnO nanoparticle aggregates up to 5 mm long appeared on the surface of the substrate. A clear free-exciton peak due to ZnO NPs is observed from these microstrip structures both in optical absorption and photoluminescence spectra.

Nanogroove formation by ion irradiation on indentation-modified amorphous SiO(2).

Ion beams are widely used for micro/nanostructure fabrication with unique features of the energetic processes. In this work, we present a self-assembled nanostructure fabrication by ion irradiation with a patterned strain/stress field. The patterned strain/stress field is introduced by micro-Vickers indentation to amorphous SiO(2) (load = 100 mN). After irradiation of 60 keV Cu(-) ions, nanogrooves (width from 150 to 250 nm) were created at the indentation edge. Under the ion irradiation of a constant ion flux, the nanogroove size linearly increased with ion fluence from 2 × 10(16) to 1.2 × 10(17) ions cm(-2). Comparison of indented samples after irradiation and thermal annealing suggests that the nanogrooving originates from ion beam interactions with residual stress/strain by indentation and that a non-thermal effect results from the ion irradiation processes. Cross-sectional TEM analysis showed that the grooves extend over 200 nm below the surface, implying that the groove growth is not caused by surface diffusion. It is concluded from the results that the grooving is due to irradiation-induced mass transport accompanied by vacancy aggregation at the interface between the indented and non-indented areas.

Dual surface plasmon resonances in Zn nanoparticles in SiO(2): an experimental study based on optical absorption and thermal stability.

Metallic zinc nanoparticles (NPs) of 5-15 nm in diameter, formed in silica glass (SiO(2)) by Zn ion implantation of 60 keV, showed a strong ultraviolet absorption peak at around 4.8 eV, which has been assigned as the surface plasmon resonance (SPR) of Zn NPs, and another small peak at 1.2 eV, which has never been reported before. To identify the origin of the 1.2 eV peak, the correlations of thermal stability between the two peaks and Zn NPs were evaluated under annealing both in a vacuum (pure thermal stability) and in oxygen gas (thermal oxidation stability). The well-correlated stability between the 1.2 eV peak, the 4.8 eV peak and Zn NPs indicates that the 1.2 eV peak is not ascribed to radiation-induced defects but to the Zn NPs. The 1.2 eV peak can be ascribed to an SPR of Zn NPs in SiO(2), because the peak satisfies the criterion of the SPR of metallic NPs. Since the 4.8 eV peak is also expected to satisfy the criterion, Zn NPs in SiO(2) have two SPRs at 1.2 and 4.8 eV.