Magneto-optical methods for magnetoplasmonics in noble metal nanostructures

The use of magneto-optical techniques to tune the plasmonic response of nanostructures is a hot topic in active plasmonics, with fascinating implications for several plasmon-based applications and devices. For this emerging field, called magnetoplasmonics, plasmonic nanomaterials with strong optical response to magnetic field are desired, which is generally challenging to achieve with pure noble metals. To overcome this issue, several efforts have been carried out to design and tailor the magneto-optical response of metal nanostructures, mainly by combining plasmonic and magnetic materials in a single nanostructure. In this tutorial we focus our attention on magnetoplasmonic effects in purely plasmonic nanostructures, as they are a valuable model system allowing for an easier rationalization of magnetoplasmonic effects. The most common magneto-optical experimental methods employed to measure these effects are introduced, followed by a review of the major experimental observations that are discussed within the framework of an analytical model developed for the rationalization of magnetoplasmonic effects. Different materials are discussed, from noble metals to novel plasmonic materials, such as heavily doped semiconductors.Comment: Tutorial article. 17 pages, 12 figure

Dielectric Effects in FeO x-Coated Au Nanoparticles Boost the Magnetoplasmonic Response: Implications for Active Plasmonic Devices

Plasmon resonance modulation with an external magnetic field (magnetoplasmonics) represents a promising route for the improvement of the sensitivity of plasmon-based refractometric sensing. To this purpose, an accurate material choice is needed to realize hybrid nanostructures with an improved magnetoplasmonic response. In this work, we prepared core@shell nanostructures made of an 8 nm Au core surrounded by an ultrathin iron oxide shell (≤1 nm). The presence of the iron oxide shell was found to significantly enhance the magneto-optical response of the noble metal in the localized surface plasmon region, compared with uncoated Au nanoparticles. With the support of an analytical model, we ascribed the origin of the enhancement to the shell-induced increase in the dielectric permittivity around the Au core. The experiment points out the importance of the spectral position of the plasmonic resonance in determining the magnitude of the magnetoplasmonic response. Moreover, the analytical model proposed here represents a powerful predictive tool for the quantification of the magnetoplasmonic effect based on resonance position engineering, which has significant implications for the design of active magnetoplasmonic devices

Star-shaped Magnetic-plasmonic Au@Fe3O4 nano-heterostructures for photothermal therapy

Here, we synthesize a Au@Fe3O4 core@shell system with a highly uniform unprecedented star-like shell morphology with combined plasmonic and magnetic properties. An advanced electron microscopy characterization allows assessing the multifaceted nature of the Au core and its role in the growth of the peculiar epitaxial star-like shell with excellent crystallinity and homogeneity. Magnetometry and magneto-optical spectroscopy revealed a pure magnetite shell, with a superior saturation magnetization compared to similar Au@Fe3O4 heterostructures reported in the literature, which is ascribed to the star-like morphology, as well as to the large thickness of the shell. Of note, Au@Fe3O4 nanostar-loaded cancer cells displayed magneto-mechanical stress under a low frequency external alternating magnetic field (few tens of Hz). On the other hand, such a uniform, homogeneous, and thick magnetite shell enables the shift of the plasmonic resonance of the Au core to 640 nm, which is the largest red shift achievable in Au@Fe3O4 homogeneous core@shell systems, prompting application in photothermal therapy and optical imaging in the first biologically transparent window. Preliminary experiments performing irradiation of a stable water suspension of the nanostar and Au@Fe3O4-loaded cancer cell culture suspension at 658 nm confirmed their optical response and their suitability for photothermal therapy. The outstanding features of the prepared system can be thus potentially exploited as a multifunctional platform for magnetic-plasmonic applications

Direct detection of spin polarization in photoinduced charge transfer through a chiral bridge

It is well assessed that the charge transport through a chiral potential barrier can result in spin-polarized charges. The possibility of driving this process through visible photons holds tremendous potential for several aspects of quantum information science, e.g., the optical control and readout of qubits. In this context, the direct observation of this phenomenon via spin-sensitive spectroscopies is of utmost importance to establish future guidelines to control photo-driven spin selectivity in chiral structures. Here, we provide direct proof that time-resolved electron paramagnetic resonance (EPR) can be used to detect long-lived spin polarization generated by photoinduced charge transfer through a chiral bridge. We propose a system comprising CdSe quantum dots (QDs), as a donor, and C60, as an acceptor, covalently linked through a saturated oligopeptide helical bridge (χ) with a rigid structure of ∼10 Å. Time-resolved EPR spectroscopy shows that the charge transfer in our system results in a C60 radical anion, whose spin polarization maximum is observed at longer times with respect to that of the photogenerated C60 triplet state. Notably, the theoretical modelling of the EPR spectra reveals that the observed features may be compatible with chirality-induced spin selectivity, but the electronic features of the QD do not allow the unambiguous identification of the CISS effect. Nevertheless, we identify which parameters need optimization for unambiguous detection and quantification of the phenomenon. This work lays the basis for the optical generation and direct manipulation of spin polarization induced by chirality

Magnetoplasmonic design rules for active magneto-optics

Light polarization rotators and non-reciprocal optical isolators are essential building blocks in photonics technology. These macroscopic passive devices are commonly based on magneto-optical Faraday and Kerr polarization rotation. Magnetoplasmonics - the combination of magnetism and plasmonics - is a promising route to bring these devices to the nanoscale. We introduce design rules for highly tunable active magnetoplasmonic elements in which we can tailor the amplitude and sign of the Kerr response over a broad spectral range

Modulation of the magnetic properties of gold-spinel ferrite heterostructured nanocrystals

The rational design of complex nanostructures is of paramount importance to gain control over their chemical and physical properties. Recently, magnetic-plasmonic heterostructured nanocrystals have been recognized as key players in nanomedicine as multifunctional therapeutic-diagnostic tools and in catalysis. Here we show how the properties of gold-iron oxide heterostructured nanocrystals can be tuned by chemical doping of the magnetic subunit. The divalent cations in the iron oxide were substituted with cobalt and manganese to obtain a general formula Au-MFe2O4 (M = Fe, Co, Mn). Magnetic properties of the heterostructures could be tuned, while maintaining well-defined plasmon resonance signatures, confirming the dual magnetic-plasmonic functional capability of these nanostructures. [Figure not available: see fulltext.]

Magnetic, optical and relaxometric properties of organically coated gold-magnetite (Au-Fe3O4) hybrid nanoparticles for potential use in biomedical applications

We presentthemagnetic,opticalandrelaxometricpropertiesofmultifunctionalAu–Fe3O4 hybrid nanoparticles(HNPs),aspossiblenovelcontrastagents(CAs)formagneticresonanceimaging(MRI). The HNPshavebeensynthesizedbywetchemicalmethodsinheterodimerandcore–shellgeometries and cappedwitholeylamine.StructuralcharacterizationofthesampleshavebeenmadebyX-ray diffractionandtransmissionelectronmicroscopy,whilemagneticpropertieshavebeeninvestigated by meansofSuperconductingQuantumInterferenceDevice-SQUIDmagnetometryexperiments. As requiredforMRIapplicationsusingnegativeCAs,thesamplesresultedsuperparamagneticatroom temperatureandwellabovetheirblockingtemperatures.Opticalpropertieshavebeeninvestigatedby analyzingtheopticalabsorbtionspectracollectedinUV–visibleregion.Relaxometricmeasurements have beenperformedonorganicsuspensionsofHNPsandNuclearMagneticResonance(NMR) dispersioncurveshavebeenobtainedbymeasuringthelongitudinal1/T1 and transverse1/T2 relaxation ratesofsolventprotonsintherange10kHz/300MHzatroomtemperature.NMRrelaxivities r1 and r2 have beencomparedwithENDOREMs, oneofthecommercialsuperparamagneticironoxidebased MRI contrastagents.MRIcontrastenhancementefficiencieshavebeeninvestigatedalsobyexamining T2-weightedMRimagesofsuspensions.Theexperimentalresultssuggestthatthenanoparticles’ suspensionsaregoodcandidatesasnegativeCAs