Disorder-induced broadening of optical vibrational eigenmodes in nanoparticles of nonpolar crystals is studied numerically. The methods previously used to treat phonons in defectless particles are adjusted for numerical evaluation of the disordered problem. Imperfections in the form of Gaussian and binary disorders as well as surface irregularities are investigated thoroughly in a wide range of impurity concentrations and disorder strengths. For dilute and weak point-like impurities the regimes of separated and overlapped phonon levels are obtained and the behavior of the linewidth predicted theoretically is confirmed, the crossover scale falls into the actual range of several nanometers. These notions survive for strong dilute impurities, as well. Regimes and crossovers predicted by theory are checked and identified, and minor discrepancies are discussed. To mention a few of them: slower than in theory increasing of the linewidth with the phonon quantum number for weak disorder and only qualitative agreement between theory and numerics for resonant broadening in strong dilute disorder. The novel phenomena discovered numerically are: "mesoscopic smearing" of distribution function in the ensemble of identical disordered particles, inflection of the linewidth dependence on the impurity concentration for light "dense" binary impurities, and position-dependent capability of strong impurity to catch the phonon. It is shown that surface irregularities contribute to the phonon linewidth less than the volume disorder, and their rate reveals faster decay with increasing of the particle size. It is argued that the results of present research are applicable also for quantum dots and short quantum wires.
Recent Raman data on diamond and crystalline Si nanopowders are analyzed with the use of a microscopic theory of Raman scattering in ensembles of disordered nonpolar nanocrystals. The large width of the Raman peak in nanoparticles as compared to the corresponding peak in bulk materials and the peak inverse dependence on the particle size observed experimentally are explained within the framework of the theory. It is shown that this theory is capable to extract confidently from the Raman data four important microscopic characteristics of the nanopowder including the mean particle size, the vari…
We calculate low-frequency Raman scattering from the confined acoustic phonon modes of CdS1-xSex nanoparticles embedded in borosilicate glass. The calculation of the Raman scattering by acoustic phonons in nanoparticles has been performed by using third-order perturbation theory. The deformation potential approximation is used to describe the electronphonon interaction. The Raman-Brillouin electronic density and the electron-phonon interaction are found to increases with decreasing size of nanoparticle. A good agreement between the calculated and reported low-frequency Raman spectra is found.
We present a microscopic model for surface-enhanced Raman scattering (SERS) from molecules adsorbed on small noble-metal nanoparticles. In the absence of direct overlap of molecular orbitals and electronic states in the metal, the main enhancement source is the strong electric field of the surface plasmon resonance in a nanoparticle acting on a molecule near the surface. In small particles, the electromagnetic enhancement is strongly modified by quantum-size effects. We show that, in nanometer-sized particles, SERS magnitude is determined by a competition between several quantum-size effects s…
We study the role of strong electron confinement in surface-enhanced Raman scattering from molecules adsorbed on small noble-metal particles. We describe a new source of Raman signal enhancement which originates from different behavior of sp-band and d-band electron densities near the particle boundary. In small particles, a spillover of sp-electron wave-functions beyond the classical radius gives rise to a thin layer with diminished population of d-electrons. In this surface layer, the screening of sp-electrons by d-band electron background is reduced. We demonstrate that the interplay betwee…
Microscopic description of Raman spectra in nanopowders of nonpolar crystals is accomplished by developing the theory of disorder-induced broadening of optical vibrational eigenmodes. Analytical treatment of this problem is performed, and line shape and width are determined as functions of phonon quantum numbers, nanoparticle shape, size, and the strength of disorder. The results are found to be strongly dependent on either the broadened line is separated or it is overlapped with other lines of the spectrum. Three models of disorder, i.e. weak point-like impurities, weak smooth random potentia…
In this letter, we propose a new model that explains the Raman peak downshift observed in nanoparticles with respect to bulk materials. The proposed model takes into account discreteness of the vibrational spectra of nanoparticles. For crystals with a cubic lattice (Diamond, Silicon, Germanium) we give a relation between the displacement of Raman peak position and the size of nanoparticles. The proposed model does not include any uncertain parameters, unlike the conventionally used phonon confinement model (PCM), and can be employed for unambiguous nanoparticles size estimation.
P-dibromobenzene nanoparticles in a case of paradihlorbenzol molecules have been synthesized. Raman spectrums of these nanoparticles are measured. At diffusion of molecules of paradihlorbenzol in a pdibromobenzene nanoparticle solid solution formed. Modifications in structure of nanoparticles at diffusion are reflected in Raman spectrums. Unlike a solid solution single crystal, in nanoparticles the accelerated diffusion, $D = 1.3 \pm 0.02 10^{-11} cm^2/s$, is observed at room temperature. Calculations show that the accelerated diffusion is caused by magnification of parametres of a lattice at …
Optical phonons in nanoparticles with the randomness of interatomic bonds are considered both analytically and numerically. For weak dilute disorder two qualitatively different regimes of separated and overlapped levels are observed, resembling the case of random atomic masses investigated previously. At stronger and/or more dense disorder, the particles become essentially inhomogeneous, thus constituting the minimal model to describe an amorphous phase, where the picture of vibrational modes becomes more subtle. We concentrate here on the experimentally relevant case of strong disorder locate…
We measured the small frequencies Raman spectrum of the paradihlorobenzene and paradihlorobenzene solid solution nanoparticles with the size about 100 nanometers. Values of frequencies of lines decrease. The size of nanoparticles was determined by the electronic microscope. Calculations of nanoparticles structure were done using the method of molecular dynamics and histograms of nanoparticles spectra were calculated via the Dyne's method. The result is that the Raman spectrum is the sum of spectra from the central part of the nanoparticle and superficial structures with smaller concentration o…
In crystalline nanoparticles the Raman peak is downshifted with respect to the bulk material and has asymmetric broadening. These effects are straightly related to the finite size of nanoparticles, giving the perspective to use the Raman spectroscopy as the size probe. By combining the dynamical matrix method (DMM) and the bond polarization model (BPM), we develop a new (DMM-BPM) approach to the description of Raman spectra for random arrays of nanoparticles. The numerical variant of this approach is suitable for the description of small particles, whereas its simplier to implement analytical …
Recent advances in our understanding of thermal transport in nanocrystalline systems are responsible for the integration of new technologies into advanced energy systems, including thermoelectric refrigeration systems and renewable energy platforms. However, there is little understanding of heat energy transport mechanisms that govern the thermal properties of disordered nanocomposites. In this work, we explore thermal transport mechanisms in disordered packings of amorphous nanoparticles with and without a polymer filling the interstices in order to quantify the impact of thermal boundary sca…
High resolution low frequency Raman scattering measurements from embedded AgAu nanoparticles unveil efficient scattering by harmonics of both the quadrupolar and the spherical modes. Comparing the experimental data with theoretical calculations that account for both the embedding medium and the resonant Raman process enables a very complete description of the observed multiple components in terms of harmonics of both the quadrupolar and spherical modes, with a dominating Raman response from the former ones. It is found that only selected harmonics of the quadrupolar mode contribute significant…
The electromagnetic enhancement for surface enhanced Raman spectroscopy (SERS) of graphene is studied by inserting a layer of Al2O3 between epitaxial graphene and Au nanoparticles. Different excitation lasers are utilized to study the relationship between laser wavelength and SERS. The theoretical calculation shows that the extinction spectrum of Au nanoparticles is modulated by the presence of graphene. The experimental results of the relationship between the excitation laser wavelength and the enhancement factor fit well with the calculated results. An exponential relationship is observed be…
Raman spectrums of nanoparticles of a p-dibromobenzene with size of 300 nanometers and 50 nanometers are measured. It is found that frequencies of lines of stretching vibrations of C-Br at reduction of the sizes of nanoparticles below 300 nanometers are incremented. It is related to magnification of parameters of the lattice and interaction reduction between molecules.
Atomically thin boron nitride (BN) nanosheets have many properties desirable for surface enhanced Raman spectroscopy (SERS). BN nanosheets have a strong surface adsorption capability towards airborne hydrocarbon and aromatic molecules. For maximized adsorption area and hence SERS sensitivity, atomically thin BN nanosheet covered gold nanoparticles have been prepared for the first time. When placed on top of metal nanoparticles, atomically thin BN nanosheets closely follow their contours so that the plasmonic hot spots are retained. Electrically insulating BN nanosheets also act as a barrier la…
We show that Nanoparticle (NP) solids are an exciting platform to seek new insights into the disordered Mott-Hubbard physics. We developed a "Hierarchical Nanoparticle Transport Simulator" (HINTS), which builds from localized states to describe the Disorder-localized and Mott-localized phases, and the transitions out of these localized phases. We also studied the interplay between correlations and disorder in the corresponding multi-orbital Hubbard model at and away from integer filling by Dynamical Mean Field Theory. This approach is complementary to HINTS, as it builds from the metallic phas…
A simple way to investigate theoretically the Raman spectra (RS) of nonpolar nanoparticles is proposed. For this aim we substitute the original lattice optical phonon eigenproblem by the continuous Klein-Fock-Gordon-like equation with Dirichlet boundary conditions. This approach provides the basis for the continuous description of optical phonons in the same manner how the elasticity theory describes the longwavelength acoustic phonons. Together with continuous reformulation of the bond polarization model it allows to calculate the RS of nanoparticles without referring to their atomistic struc…
Single-molecule surface enhanced Raman scattering (SM-SERS) is one of the vital applications of plasmonic nanoparticles. The SM-SERS sensitivity critically depends on plasmonic hot-spots created at the vicinity of such nanoparticles. In conventional fluid-phase SM-SERS experiments, plasmonic hot-spots are facilitated by chemical aggregation of nanoparticles. Such aggregation is usually irreversible, and hence, nanoparticles cannot be re-dispersed in the fluid for further use. Here, we show how to combine SM-SERS with plasmon-polariton assisted, reversible assembly of plasmonic nanoparticles at…
Surface enhanced Raman scattering (SERS) exploits surface plasmons induced by the incident field in metallic nanostructures to significantly increase the Raman intensity. Graphene provides the ideal prototype two dimensional (2d) test material to investigate SERS. Its Raman spectrum is well known, graphene samples are entirely reproducible, height controllable down to the atomic scale, and can be made virtually defect-free. We report SERS from graphene, by depositing arrays of Au particles of well defined dimensions on graphene/SiO$_2$(300nm)/Si. We detect significant enhancements at 633nm. To…
Thin films of uniformly distributed Fe2O3 nanoparticles have been prepared on single crystal silicon and glass substrates by a spray pyrolysis technique in a single step using a mixture of water and ferrocene dissolved in xylene. The size distribution of nanoparticles is found to be in the range of 20 nm to 30 nm. The films have been characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy techniques. The uniformity of the grown film was evident from the electron microscopic images on both the substrates. The crystallinity and band gap were investigated using X-r…
Using Raman scattering, the solid solution nanoparticles of paradibrombenzol/paradihlorbenzol are investigated. It is found that in a spectrum of nanoparticles of solid solution frequencies of spectral lines are reduced in comparison with similar lines of a single crystal with the same concentration of components. Calculations of the lattice oscillations by Dyne's method are performed. It is shown that these modifications of frequencies can be caused by the increase of lattice parameters with the reduction of nanoparticles sizes.
We present a simple method to prove the presence of an organic shell around silver nanoparticles. This method is based on the comparison between optical extinction measurements of isolated nanoparticles and Mie calculations predicting the expected wavelength of the Localized Surface Plasmon Resonance of the nanoparticles with and without the presence of an organic layer. This method was applied to silver nanoparticles which seemed to be well protected from oxidation. Further experimental characterization via Surface Enhanced Raman Spectroscopy (SERS) measurements allowed to identify this prote…
Controlled wrinkling of single-layer graphene (1-LG) at nanometer scale was achieved by introducing monodisperse nanoparticles (NPs), with size comparable to the strain coherence length, underneath the 1-LG. Typical fingerprint of the delaminated fraction of 1-LG is identified as substantial contribution to the principal Raman modes of the 1-LG. Correlation analysis of the Raman shift of the modes clearly resolved the 1-LG in contact and delaminated from the substrate, respectively. Intensity of Raman features of the delaminated 1-LG increases linearly with the amount of the wrinkles, determin…
Herein we report experimental evidence of directional SERS from molecules situated inside a single nanowire-nanoparticle junction cavity. The emission was confined to a narrow range of wavevectors perpendicular to the axis of the cavity. In addition to this, the molecules excite multiple guided modes of the nanowire which were imaged using leakage radiation Fourier microscopy. We further characterize the emission wavevectors as a function of output polarization. The excited guided modes of the wire show interesting polarization signatures. All the results were corroborated using finite element…
Graphene covered metal nanoparticles constitute a novel type of hybrid materials, which provide a unique platform to study plasmonic effects, surface-enhanced Raman scattering (SERS), and metal-graphene interactions at the nanoscale. Such a hybrid material is fabricated by transferring graphene grown by chemical vapor deposition onto closely spaced gold nanoparticles produced on a silica wafer. The morphology and physical properties of nanoparticle-supported graphene is investigated by atomic force microscopy, optical reflectance spectroscopy, scanning tunneling microscopy and spectroscopy (ST…
Terahertz time domain spectroscopy has been used to study low frequency confined acoustic phonons of silver nanoparticles embedded in poly(vinyl alcohol) matrix in the spectral range of 0.1 to 2.5 THz. The real and imaginary parts of the dielectric function show two bands at 0.60 THz and 2.12 THz attributed to the spheroidal and toroidal modes of silver nanoparticles, thus demonstrating the usefulness of terahertz time domain spectroscopy as a complementary technique to Raman spectroscopy in characterizing the nanoparticles.
Raman scattering (RS) spectra and current-voltage characteristics at room temperature were measured in six series of small samples fabricated by means of electron-beam lithography on the surface of a large size (5x5 mm) industrial monolayer graphene film. Samples were irradiated by different doses of C${}^+$ ion beam up to $10^{15}$ cm${}^{-2}$. It was observed that at the utmost degree of disorder, the Raman spectra lines disappear which is accompanied by the exponential increase of resistance and change in the current-voltage characteristics.These effects are explained by suggestion that hig…
Exchange bias effects linked to surface spin freezing (SSF) are commonly found in iron oxide nanoparticles, while signatures of SSF in low-field temperature-dependent magnetization curves have been much less frequently reported. Here, we present magnetic properties of dense assemblies of similar-sized (~ 8 nm diameter) particles synthesized by a magnetite (sample S1) and a maghemite (sample S2) method, and the influence of long-term (4-year) sample aging under ambient conditions on these properties. The size of the exchange bias field of the different sample (fresh or aged) states is found to …
We analyze the transport in disordered two-dimensional nanoparticle arrays. We show that the commonly used scaling hypothesis to fit the I-V curves does not describe the electronic transport in these systems. On the contrary, close to the threshold voltage V_T the current depends linearly on (V-V_T). This linear behavior is observed for at least five decades in (V-V_T). Fitting the I-V curves at larger voltages to a scaling power-law I \propto (V/V_T-1)^ξresults in fitting parameters which depend on the range of voltages used and in wrong values for V_T. Our results urge to change the picture …
We study the interplay between disorder and topology for the localized edge states of light in topological zigzag arrays of resonant dielectric nanoparticles. We characterize topological properties by the winding number that depends on both zigzag angle and spacing between nanoparticles in the array. For equal-spacing arrays, the system may have two values of the winding number $ν=0$ or $1$, and it demonstrates localization at the edges even in the presence of disorder, being consistent with experimental observations for finite-length nanodisk structures. For staggered-spacing arrays, the syst…
Revealing hidden non-radiative (dark) of resonant nanostructures using optical methods such as dark-field spectroscopy often becomes a sophisticated problem due to a weak coupling of these modes with a far-field radiation, whereas methods of dark-modes spectroscopy, e.g. cathodoluminescence or elastic energy losses, are not always convenient in use. Here, we suggest an approach for experimental determining the mode structure of a nanoresonator basing on utilizing intrinsic incoherent Raman scattering. We theoretically predict the efficiency of this approach and realize it experimentally for si…
Chemical techniques are an efficient method to synthesize one-dimensional perovskite manganite oxide nanostructures with a granular morphology, that is, formed by arrays of monodomain magnetic nanoparticles. Integrating the stochastic Landau-Lifshitz-Gilbert equation, we simulate the dynamics of a simple disordered model for such materials that only takes into account the morphological characteristics of their nanograins. We show that it is possible to describe reasonably well experimental hysteresis loops reported in the literature for single La_0.67Ca_0.33MnO_3 nanotubes and powders of these…
Acoustic vibrations of nanoparticles made of materials with anisotropic elasticity and nanoparticles with non-spherical shapes are theoretically investigated using a homogeneous continuum model. Cubic, hexagonal and tetragonal symmetries of the elasticity are discussed, as are spheroidal, cuboctahedral and truncated cuboctahedral shapes. Tools are described to classify the different vibrations and for example help identify the modes having a significant low-frequency Raman scattering cross-section. Continuous evolutions of the modes starting from those of an isotropic sphere coupled with the d…
Integrating graphene with plasmonic nanostructures results in multifunctional hybrid systems with enhanced performance for numerous applications. In this work, we take advantage of the remarkable mechanical properties of graphene to combine it with scalable 3D plasmonic nanostructured silicon substrates, which enhance the interaction of graphene with electromagnetic radiation. Large areas of femtosecond laser-structured arrays of silicon nanopillars, decorated with gold nanoparticles, are integrated with graphene, which conforms to the substrate nanotopography. We obtain Raman spectra at 488, …
The Raman scattering spectra (RS) of two series of monolayer graphene samples irradiated with various doses of C$^{+}$ and Xe$^{+}$ ions were measured after annealing in high vacuum, and in forming gas (95\%Ar+5\%H$_{2}$). It was found that these methods of annealing have dramatically different influence on the RS lines. Annealing in vacuum below 500$^{\circ}$C leads to significant decrease of both D-line, associated with defects, and 2D-line, associated with the intact lattice structure, which can be explained by annealing-induced enhanced doping. Further annealing in vacuum up to 1000$^{\cir…
In this paper, we establish the existence of both compressive stress and charge transfer process in hydrothermally synthesized cobalt ferrite-graphene oxide (CoFe2O4/GO) nanocomposites. Transmission electron microscopy (TEM) results reveal the decoration of CoFe2O4 nanoparticles on GO sheets. Magnetic response of nanocomposites was confirme from superconducting quantum interference device (SQUID) magnetometer measurement. Optical properties of these nanocomposites were investigated by Raman spectroscopy. Interfacial compressive stress involved in this system is evaluated from observed blue shi…
We investigated the relative stability of the amorphous vs crystalline nanoparticles of size ranging between 0.8 and 1.8 nm. We found that, at variance from bulk systems, at low T small nanoparticles are amorphous and they undergo to an amorphous-to-crystalline phase transition at high T. On the contrary, large nanoparticles recover the bulk-like behavior: crystalline at low T and amorphous at high T. We also investigated the structure of crystalline nanoparticles, providing evidence that they are formed by an ordered core surrounded by a disordered periphery. Furthermore, we also provide evid…
Nanomaterials capable of confining light are desirable for enhancing spectroscopies such as Raman scattering, infrared absorption, and nonlinear optical processes. Plasmonic superlattices have shown the ability to host collective resonances in the mid-infrared, but require stringent fabrication processes to create well-ordered structures. Here, we demonstrate how short-range-ordered Au nanoparticle multilayers on a mirror, self-assembled by a sub-nm molecular spacer, support collective plasmon-polariton resonances in the visible and infrared, continuously tunable beyond 11 $μ$m by simply varyi…
