Light absorption and scattering of plasmonic metal nanoparticles can lead to non-equilibrium charge carriers, intense electromagnetic near-fields, and heat generation, with promising applications in a vast range of fields, from chemical and physical sensing, to nanomedicine, and photocatalysis for the sustainable production of fuels and chemicals. Disentangling the relative contribution of thermal and non-thermal contributions in plasmon driven processes is however difficult. Nanoscale temperature measurements are technically challenging and macroscale experiments are often characterized by collective heating effects, which tend to make the actual temperature increase unpredictable. This work is intended to help the reader experimentally detect and quantify photothermal effects in plasmon-driven chemical reactions, to discriminate their contribution from the one due to photochemical processes, and to cast a critical eye on the current literature. To this aim, we review, and in some cases propose, seven simple experimental procedures, which do not require the use of complex or expensive thermal microscopy techniques. These proposed procedures are adaptable to a wide range of experiments and fields of research where photothermal effects need to be assessed, such as plasmonic-assisted chemistry, heterogeneous catalysis, photovoltaics, biosensing and enhanced molecular spectroscopy.
Gold nanospheres (Au NSs) and gold nanorods (Au NRs) are traditional noble metal plasmonic nanomaterials. Particularly, Au NRs with tunable longitudinal plasmon resonance from visible to the near infrared (NIR) range were suitable for high efficient photothermal applications due to extended light receiving range. In this work, we synthesized Au NRs and Au NSs of similar volume, and subsequently developed them into Au NR/PVDF and Au NS/PVDF nanofilm, both of which exhibited excellent solar photothermal performance evaluated by solar photothermal experiments. We found that Au NR/PVDF nanofilm sh…
We theoretically investigate equilibrium behaviors and photothermal effects of a flexible plasmonic metamaterial composed of aramid nanofibers and gold nanoparticles. The fiber matrix is considered as an external field to reconfigure a nanoparticle assembly. We find that the heating process tunes particle-particle and fiber-particle interactions, which alter adsorption of nanoparticles on fiber surfaces or clustering in pore spaces. Thus, it is possible to control the nanoparticle self-assembly by laser illumination. Gold nanoparticles strongly absorb radiations and efficiently dissipate absor…
Longer near-infrared wavelengths provide better penetration depth in biological tissues, so these are useful for plasmonic photothermal cancer therapeutics. In the context of nanoparticles for such applications, the absorption can be tuned for longer NIR wavelengths. However, on increasing the size of the nanoparticle, the scattering is enhanced and thus is not suitable for plasmonic therapeutics. Therefore, to overcome this issue, different types of small gold nanorods were synthesized and converted into stable aggregates to red-shift the plasmonic resonance wavelength to longer near-infrared…
While the thermal and electromagnetic properties of plasmonic nanostructures are well understood, nanoscale thermometry still presents an experimental and theoretical challenge. Plasmonic structures can confine electromagnetic energy at the nanoscale, resulting in local, inhomogeneous, controllable heating. But reading out the temperature with nanoscale precision using optical techniques poses a difficult challenge. Here we report on the optical thermometry of individual gold nanorod trimers that exhibit multiple wavelength-dependent plasmon modes resulting in measurably different local temper…
We demonstrate the direct photothermal probing and mapping of single plasmonic nanostructures via the temperature induced detuning of nanomechanical string resonators. Single Au nanoslits are illuminated with a low-power polarized focused laser beam (λ = 633 nm). Polarization dependent heat generation in gold nanoslits is then imaged with high sensitivity. A sensitivity of -4.1 ppm/nW with respect to the illuminated light (beam diameter 5.0pm0.8 μm) is determined for a single nanoslit (1 μm long and 53 nm wide), which equals to a total light absorption of 16%. This results in a heating of 0.5 …
The photothermal energy conversion in hanging and floating polyaniline (PANi)-cotton fabrics is investigated using a model based on the heat diffusion equation. Perfect absorption and anti-reflection of wet hanging PANi-cotton fabrics cause quick transfer of total incident light into water confining nearly 100 $\%$ of the sunlight. As a result, a hanging membrane is found to have more attractive properties than a floating above water fabric. We find, however, that the photothermal properties of a floating PANi-cotton membrane can greatly be enhanced by dispersing TiN nanoparticles in the water…
The recently reported 3rd and 4th biological transparency windows located respectively at 1.6-1.9um and 2.1-2.3um promise deeper tissue penetration and reduced collateral photodamage, yet they haven't been utilized in photothermal therapy applications. Nanoparticle based plasmonic photothermal therapy poses a nontrivial optimization problem in which the light absorption efficiency of the nanoparticle has to be maximized subject to various constraints that are imposed by application environment. Upscaling the typical absorber-dominant nanoparticle designs (rod, sphere etc.) that operate in the …
Bimetallic plasmonic nanoparticles enable tuning of the optical response and chemical stability by variation of the composition. The present numerical simulation study compares Ag-Au alloy, Ag@Au core-shell, and Au@Ag core-shell bimetallic plasmonic nanoparticles of both spherical and anisotropic (nanotriangle and nanorods) shapes. By studying both spherical and anisotropic (with LSPR in the near-infrared region) shapes, cases with and without interband transitions of Au can be decoupled. Explicit comparisons are facilitated by numerical models supported by careful validation and examination o…
Thermonanophotonics, i.e. the study of photothermal effects in optical nanoantennas, has recently attracted growing interest. While thermoplasmonic structures enable a broad range of applications, from imaging and optofluidics devices to medical and photochemical systems, dielectric nanoantennas open new opportunities for thermo-optical modulation and reconfigurable metasurfaces. However, computing both photo-thermal and thermo-optical effects in large arrays of nanoantennas remains a challenge. In this work, we implement a fast numerical method to compute the temperature increase of multi-dim…
Proximity of the metal nanoparticles enhance the plasmonic coupling and shifts the resonance. This article presents a numerical study of the photothermal effect in aggregates of small gold nanorods considering the ordered as well as random aggregates. In the ordered aggregates, there is lateral coupling which causes blueshifts in the plasmonic resonance, while in the random aggregates there are redshifts in the plasmonic resonance. The plasmon response of latter could be tailored up to the second infrared biological therapeutic window. It has been observed that the aggregates show higher absor…
Photothermal spectroscopy and microscopy provides a route to measure the spectral and spatial properties of individual nanoscopic absorbers, independent from scattering, extinction, and emission. The approach relies upon use of two light sources, one that resonantly excites and heats the target and its surrounding environment and a second off-resonant probe that scatters from the resulting volume of thermally modified refractive index. Over the past twenty years, considerable effort has been extended to apply photothermal methods to detect, spatially resolve, and perform absorption spectroscop…
Fundamental limits of hot-carrier and photothermal plasmonic solar chemistry
KU-KIST Graduate School of Converging Science and Technology, Korea University（韩中研究生融合科学与技术学院，韩国大学）；Department of Integrative Energy Engineering (College of Engineering) and Department of Biomicrosystem Technology, Korea University（韩国大学集成能源工程系（工程学院）和生物微系统技术系）
Photothermal surface bubbles play important roles in a wide range of applications like catalysis, microfluidics and biosensing, but their formation on a transparent substrate immersed in a plasmonic nanoparticle (NP) suspension has an unknown origin. Here, we show that NPs deposited on the substrate by dispersive optical forces are responsible for the nucleation of such photothermal surface bubbles. High-speed videography shows that the surface bubble formation is always preceded by the optically driven NPs moving toward and adhering to the surface. We observe that the thresholds of laser powe…
Optical properties of colloidal plasmonic titanium nitride nanoparticles are examined with an eye on their photothermal via transmission electron microscopy and optical transmittance measurements. Single crystal titanium nitride cubic nanoparticles with an average size of 50 nm exhibit plasmon resonance in the biological transparency window. With dimensions optimized for efficient cellular uptake, the nanoparticles demonstrate a high photothermal conversion efficiency. A self-passivating native oxide at the surface of the nanoparticles provides an additional degree of freedom for surface funct…
Janus particles have flourished as subject of intensive research due to their synergetic properties and their promising use in different fields, especially in biomedicine. The combination of materials with radically different physical properties in the same nanostructure gives rise to the so-called Janus effects, allowing phenomena of a contrasting nature to occur in the same architecture. In particular, interesting advantages can be taken from a thermal Janus effect for photoinduced hyperthermia cancer therapies. Such therapies still have limitations associated to the heating control in terms…
Assemblies of closely separated gold nanoparticles exhibit a strong collective plasmonic response due to coupling of the plasmon modes of the individual nanostructures. In the context of self-assembly of nanoparticles, closed packed 2D clusters of spherical nanoparticles present an important composite system that promises numerous applications. The present study probes the collective plasmonic characteristics and resulting photothermal behavior of closed packed 2D Au nanoparticle clusters in order to delineate the effects of cluster size, inter-particle distance and particle size. Smaller nano…
It is now well established that, due to excitation of localized surface plasmon resonances in plasmonic nanosystems, the electric field from an external irradiation source is greatly amplified in their vicinity. Surface plasmon mediated electric field amplification near plasmonic nanosystems is of vital importance for; light absorption enhancement of solar cells, molecular detection using surface enhanced Raman spectroscopy, proximity measurement of biological macromolecules such as proteins, lipids and nucleic acids using plasmon enhanced FRET, cancer therapy using photothermal effects, just …
Light-assisted micro-nanoscale temperature control in complex nanoparticle network attracts lots of research interests. Many efforts have been put on the optical properties of the nanoparticle networks and only a few investigations on its light-induced thermal behavior was reported. We consider two-dimensional (2D) square-lattice nanoparticle ensemble made of typical metal Ag with a radius of 5 nm. The effect of complex optical coupling and thermal accumulation on the light-induced thermal behavior in plasmonic resonance frequency (around 383 nm) is analyzed by means of the Green\textquotesing…
We theoretically investigate photothermal heating of ultra-flexible metamaterials, which are obtained by randomly mixing TiN nanoparticles in polydimethylsiloxane (PDMS). Due to the plasmonic properties of TiN nanoparticles, incident light is perfectly absorbed in a broadband range (300-3000 nm) to generate heat within these metamaterials. Under irradiation of an 808 nm near-infrared laser with different intensities, our predicted temperature rises as a function of time agree well with recent experimental data. For a given laser intensity, the temperature rise varies non-monotonically with con…
We report here chiroptical amplification effect occurring in the hybrid systems consisting of chiral molecules and Si nanostructures. Under resonant excitation of circularly polarized light, the hybrid systems show strong CD induction signals at optical frequency, which arise from both the electric and magnetic responses of the Si nanostructures. More interestingly, the induced CD signals from Si-based dielectric nanoantennas are always larger than that from Au-based plasmonic counterparts. The related physical origin was disclosed. Furthermore, compared to the Au-based high-loss plasmonic nan…
Plasmonic catalysis holds significant promise for opening new reaction pathways inaccessible thermally, or for improving the efficiency of chemical processes. However, challenges persist in distinguishing photothermal effects from effects due to energetic electrons and/or holes excited in the metal comprising a plasmonic structure. Here we use a Au stripe waveguide along which surface plasmon polaritons (SPPs) propagate, operating simultaneously as a working electrode in a 3-electrode electrochemical cell. Cyclic voltammograms were obtained under SPP excitation as a function of incident optica…
The search for the signature of non-thermal (so-called ``hot'') electrons in illuminated plasmonic nanostructures requires a detailed understanding of the non-equilibrium electron distribution under illumination, as well as a careful design of the experimental system employed to distinguish non-thermal electrons from thermal ones. Here, we provide a theory for using plasmonic molecular junctions to achieve this goal. We show how non-thermal electrons can be measured directly and separately from the unavoidable thermal response, and discuss the relevance of our theory to recent experiments.
Universal imprinting of chirality with chiral light by employing plasmonic metastructures
Ohio University（俄亥俄大学）；Nanoscale and Quantum Phenomena Institute, Ohio University（俄亥俄大学纳米尺度与量子现象研究所）；Edison Biotechnology Institute, Ohio University（俄亥俄大学爱迪生生物技术研究所）；Departamento de Tecnología médica, Facultad de Medicina, Universidad de Chile（智利大学医学院医学技术系）；CINBIO, Universidade de Vigo（维戈大学生物界面化学中心）；Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China（电子科技大学前沿与基础科学研究所）；School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University（特拉维夫大学雷蒙德和贝弗利·萨克勒理学院化学系）
Surface plasmon enhanced processes and hot-carrier dynamics in plasmonic nanostructures are of great fundamental interest to reveal light-matter interactions at the nanoscale. Using plasmonic tunnel junctions as a platform supporting both electrically- and optically excited localized surface plasmons, we report a much greater (over 1000x) plasmonic light emission at upconverted photon energies under combined electro-optical excitation, compared with electrical or optical excitation separately. Two mechanisms compatible with the form of the observed spectra are interactions of plasmon-induced h…
Plasmonic resonances in metallic nanostructures have been shown to drastically enhance local electromagnetic fields, and thereby increase the efficiency of nonlinear optical phenomena, such as second harmonic generation (SHG). While it has been experimentally observed that enhanced fields can significantly boost SHG, to date it proved difficult to probe electrical and magnetic resonances in one and the same nanostructure. This however is necessary to directly compare relative contributions of electrical and magnetic components of SHG enhancement. In this paper we report an experimental study o…
Recent advances in Nanotechnologies have prompted the need for tools to accurately and non-invasively manipulate individual nano-objects. Among possible strategies, optical forces have been foreseen to provide researchers with nano-optical tweezers capable to trap a specimen and move it in 3D. In practice though, the combination of weak optical forces involved and photothermal issues have thus far prevented their experimental realization. Here, we demonstrate first 3D optical manipulation of single 50 nm dielectric objects with near field nano-tweezers. The nano-optical trap is built by engine…
Plasmonic nanostructures attract tremendous attention as they confine electromagnetic fields well below the diffraction limit while simultaneously sustaining extreme local field enhancements. To fully exploit these properties, the identification and classification of resonances in such nanostructures is crucial. Recently, a novel figure of merit for resonance classification has been proposed 1 and its applicability was demonstrated mostly to toy model systems. This novel measure, the energy-based plasmonicity index (EPI), characterizes the nature of resonances in molecular nanostructures. The …
The theory to calculate circular dichroism (CD) of chiral molecules in a finite cluster with arbitrarily disposed objects has been developed by means of T-matrix method. The interactions between chiral molecules and nanostructures have been investigated. Our studies focus on the case of chiral molecules inserted into plasmonic hot spots of nanostructures. Our results show that the total CD of the system with two chiral molecules is not sum for two cases when two chiral molecules inserted respectively into the hot spots of nanoparticle clusters as the distances among nanoparticles are small, al…
Optical extinction and near-field properties of plasmonic dimers: Role of particle shape and separation
Max-Born-Institut（马克斯·伯恩研究所）；Institut für Physik, Humboldt-Universität zu Berlin（柏林洪堡大学物理研究所）；Institute of Condensed Matter Theory and Optics, Friedrich-Schiller-University Jena（耶拿弗里德里希·席勒大学凝聚态理论与光学研究所）
