Memristive Control of Plasmon-Mediated Nonlinear Photoluminescence in Au Nanowires.

Nonlinear photoluminescence (N-PL) is a broadband photon emission arising from a nonequilibrium heated electron distribution generated at the surface of metallic nanostructures by ultrafast pulsed laser illumination. N-PL is sensitive to surface morphology, local electromagnetic field strength, and electronic band structure, making it relevant to probe optically excited nanoscale plasmonic systems. It also has been key to accessing the complex multiscale time dynamics ruling electron thermalization. Here, we show that plasmon-mediated N-PL emitted by a gold nanowire can be modified by an electrical architecture featuring a nanogap. Upon voltage activation, we observe that N-PL becomes dependent on the electrical transport dynamics and can thus be locally modulated. This finding brings an electrical leverage to externally control the photoluminescence generated from metal nanostructures and constitutes an asset for the development of emerging nanoscale interface devices managing photons and electrons.

Long and isolated graphene nanoribbons by on-surface polymerization on Au(111).

Low electronic gap graphene nanoribbons (GNRs) are used for the fabrication of nanomaterial-based devices and, when isolated, for mono-molecular electronics experiences, for which a well-controlled length is crucial. Here, an on-surface chemistry protocol is monitored for producing long and well-isolated GNR molecular wires on an Au(111) surface. The two-step Ullmann coupling reaction is sequenced in temperature from 100 °C to 350 °C by steps of 50 °C, returning at room temperature between each step and remaining in ultrahigh vacuum conditions. After the first annealing step at 100 °C, the monomers self-organize into 2-monolayered nano-islands. Next, the Ullmann coupling reaction takes place in both 1st and 2nd layers of those nano-islands. The nano-island lateral size and shape are controlling the final GNR lengths. Respecting the above on-surface chemistry protocol, an optimal initial monomer coverage of ~1.5 monolayer produces isolated GNRs with a final length distribution reaching up to 50 nm and a low surface coverage of ~0.4 monolayer suitable for single molecule experiments.

Engineering of brick and staple components for ordered assembly of synthetic repeat proteins.

Synthetic ɑRep repeat proteins are engineered as Brick and Staple protein pairs that together self-assemble into helical filaments. In most cases, the filaments spontaneously form supercrystals. Here, we describe an expanded series of ɑRep Bricks designed to stabilize the interaction between consecutive Bricks, to control the length of the assembled multimers, or to alter the spatial distribution of the Staple on the filaments. The effects of these Brick modifications on the assembly, on the final filament structure and on the crystal symmetry are analyzed by biochemical methods, electron microscopy and small angle X-ray scattering. We further extend the concept of Brick/Staple protein origami by designing a new type of "Janus"-like Brick protein that is equally assembled by orthogonal staples binding its inner or outer surfaces and thus ending inside or outside the filaments. The relative roles of longitudinal and lateral associations in the assembly process are discussed. This set of results demonstrates important proofs-of-principle for engineering these remarkably versatile proteins toward nanometer-to-micron scale constructions.

Design, synthesis, and characterization of protein origami based on self-assembly of a brick and staple artificial protein pair.

A versatile strategy to create an inducible protein assembly with predefined geometry is demonstrated. The assembly is triggered by a binding protein that staples two identical protein bricks together in a predictable spatial conformation. The brick and staple proteins are designed for mutual directional affinity and engineered by directed evolution from a synthetic modular repeat protein library. As a proof of concept, this article reports on the spontaneous, extremely fast and quantitative self-assembly of two designed alpha-repeat (αRep) brick and staple proteins into macroscopic tubular superhelices at room temperature. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM with staining agent and cryoTEM) elucidate the resulting superhelical arrangement that precisely matches the a priori intended 3D assembly. The highly ordered, macroscopic biomolecular construction sustains temperatures as high as 75 °C thanks to the robust αRep building blocks. Since the α-helices of the brick and staple proteins are highly programmable, their design allows encoding the geometry and chemical surfaces of the final supramolecular protein architecture. This work opens routes toward the design and fabrication of multiscale protein origami with arbitrarily programmed shapes and chemical functions.

Structural identification of graphene films and nanoislands on 6H-SiC(0001) by direct height measurement.

By combining non-contact atomic force microscopy (nc-AFM) and Kelvin probe microscopy (KPFM) in ultra high vacuum environment (UHV), we directly measure the height and work function of graphene monolayer on the Si-face of 6H-SiC(0001) with a precision that allows us to differentiate three different types of graphene structures : zero layer graphene (ZLG), Quasi free-standing monolayer graphene (QFMLG) and bilayer graphene (BLG). The height and work function of ZLG are 2.62 ± 0.22 Å and 4.42 ± 0.05 eV respectively, when they are 4.09 ± 0.11 Å and 4.63 ± 0.05 eV for QFMLG. The work function is 4.83 ± 0.05 eV for the BLG. Unlike any other available technique, the local nc-AFM/KPFM dual probe makes it possible to directly identify the nature of nanometer-sized graphene islands that constitute the early nuclei of graphene monolayer grown on 6H-SiC(0001) by chemical vapor deposition.

Coherent two-beam steering of delocalized nonlinear photoluminescence in a plasmon cavity.

We aim at controlling the spatial distribution of nonlinear photoluminescence in a shaped micrometer-size crystalline gold flake. Interestingly, the underlying surface plasmon modal landscape sustained by this mesoscopic structure can be advantageously used to generate nonlinear photoluminescence (nPL) in remote locations away from the excitation spot. By controlling the modal pattern, we show that the delocalized nonlinear photoluminescence intensity can be redistributed spatially. This is first accomplished by changing the polarization orientation of the pulsed laser excitation in order to select a subset of available surface plasmon modes within a continuum. We then propose a second approach to redistribute the nPL within the structure by implementing a phase control of the plasmon interference pattern arising from a coherent two-beam excitation. Control and engineering of the nonlinear photoluminescence spatial extension is a prerequisite for deploying the next generation of plasmonic-enabled integrated devices relying on hot carriers.

Interconnect-Free Multibit Arithmetic and Logic Unit in a Single Reconfigurable 3 µm2 Plasmonic Cavity.

Processing information with conventional integrated circuits remains beset by the interconnect bottleneck: circuits made of smaller active devices need longer and narrower interconnects, which have become the prime source of power dissipation and clock rate saturation. Optical interchip communication provides a fast and energy-saving option that still misses a generic on-chip optical information processing by interconnect-free and reconfigurable Boolean arithmetic logic units (ALU). Considering metal plasmons as a platform with dual optical and electronic compatibilities, we forge interconnect-free, ultracompact plasmonic Boolean logic gates and reconfigure them, at will, into computing ALU without any redesign nor cascaded circuitry. We tailor the plasmon mode landscape of a single 2.6 µm2 planar gold cavity and demonstrate the operation and facile reconfiguration of all 2-input logic gates. The potential for higher complexity of the same logic unit is shown by a multi-input excitation and a phase control to realize an arithmetic 2-bit adder.

Single plasmon spatial and spectral sorting on a crystalline two-dimensional plasmonic platform.

In the context of the emerging field of quantum plasmonics, we demonstrate in this manuscript the wavelength-dependent propagation and sorting of single plasmons launched in a two-dimensional crystalline gold flake by a broadband quantum nanoemitter. The stream of single plasmons in the visible is produced by a nanodiamond hosting a single nitrogen-vacancy color center positioned in the near field of the mesoscopic metallic microplatelet. Spatially and spectrally resolved images of the single plasmon propagation in the pristine hexagonal flake, and then in the same structure after insertion of a Bragg mirror, are obtained by filtered image-plane acquisitions on a leakage-radiation microscope. Our work on two-dimensional crystalline structures paves the way to future fundamental studies and applications in quantum plasmonics.

Hybrid gold nanoparticle-quantum dot self-assembled nanostructures driven by complementary artificial proteins.

Hybrid nanostructures are constructed by the direct coupling of fluorescent quantum dots and plasmonic gold nanoparticles. Self-assembly is directed by the strong affinity between two artificial α-repeat proteins that are introduced in the capping layers of the nanoparticles at a controlled surface density. The proteins have been engineered to exhibit a high mutual affinity, corresponding to a dissociation constant in the nanomolar range, towards the protein-functionalized quantum dots and gold nanoparticles. Protein-mediated self-assembly is evidenced by surface plasmon resonance and gel electrophoresis. The size and the structure of colloidal superstructures of complementary nanoparticles are analyzed by transmission electron microscopy and small angle X-ray scattering. The size of the superstructures is determined by the number of proteins per nanoparticle. The well-defined geometry of the rigid protein complex sets a highly uniform interparticle distance of 8 nm that affects the emission properties of the quantum dots in the hybrid ensembles. Our results open the route to the design of hybrid emitter-plasmon colloidal assemblies with controlled near-field coupling and better optical response.

Directed evolution of artificial repeat proteins as habit modifiers for the morphosynthesis of (111)-terminated gold nanocrystals.

Natural biocomposites are shaped by proteins that have evolved to interact with inorganic materials. Protein directed evolution methods which mimic Darwinian evolution have proven highly successful to generate improved enzymes or therapeutic antibodies but have rarely been used to evolve protein-material interactions. Indeed, most reported studies have focused on short peptides and a wide range of oligopeptides with chemical binding affinity for inorganic materials have been uncovered by phage display methods. However, their small size and flexible unfolded structure prevent them from dictating the shape and crystallinity of the growing material. In the present work, a specific set of artificial repeat proteins (αRep), which exhibit highly stable 3D folding with a well-defined hypervariable interacting surface, is selected by directed evolution of a very efficient home-built protein library for their high and selective affinity for the Au(111) surface. The proteins are built from the extendable concatenation of self-compatible repeated motifs idealized from natural HEAT proteins. The high-yield synthesis of Au(111)-faceted nanostructures mediated by these αRep proteins demonstrates their chemical affinity and structural selectivity that endow them with high crystal habit modification performances. Importantly, we further exploit the protein shell spontaneously assembled on the nanocrystal facets to drive protein-mediated colloidal self-assembly and on-surface enzymatic catalysis. Our method constitutes a generic tool for producing nanocrystals with determined faceting, superior biocompatibility and versatile bio-functionalization towards plasmon-based devices and (bio)molecular sensors.

Selective excitation of surface plasmon modes propagating in Ag nanowires.

Surface plasmon modes propagating in metal nanowires are conveniently excited by focusing a laser beam on one extremity of the nanowire. We find that the precise positioning of the nanowire inside the focal region drastically influences the excitation efficiency of the different SPP modes sustained by the plasmonic waveguide. We demonstrate a spatially selective excitation of bound and leaky surface plasmon modes with excitation maps that strongly depend on the orientation of the incident linear polarization. We discuss this modal selection by considering the inhomogeneous distribution of the field components inside the focus. Our finding provides a way to discriminate the effective indices of the modes offering thus an increased coupling agility for future nanowire-based plasmonic architectures.

Wettability of partially suspended graphene.

The dependence of the wettability of graphene on the nature of the underlying substrate remains only partially understood. Here, we systematically investigate the role of liquid-substrate interactions on the wettability of graphene by varying the area fraction of suspended graphene from 0 to 95% by means of nanotextured substrates. We find that completely suspended graphene exhibits the highest water contact angle (85° ± 5°) compared to partially suspended or supported graphene, regardless of the hydrophobicity (hydrophilicity) of the substrate. Further, 80% of the long-range water-substrate interactions are screened by the graphene monolayer, the wettability of which is primarily determined by short-range graphene-liquid interactions. By its well-defined chemical and geometrical properties, supported graphene therefore provides a model system to elucidate the relative contribution of short and long range interactions to the macroscopic contact angle.

Nanoparticles Self-Assembly Driven by High Affinity Repeat Protein Pairing.

Proteins are the most specific yet versatile biological self-assembling agents with a rich chemistry. Nevertheless, the design of new proteins with recognition capacities is still in its infancy and has seldom been exploited for the self-assembly of functional inorganic nanoparticles. Here, we report on the protein-directed assembly of gold nanoparticles using purpose-designed artificial repeat proteins having a rigid but modular 3D architecture. αRep protein pairs are selected for their high mutual affinity from a library of 10(9) variants. Their conjugation onto gold nanoparticles drives the massive colloidal assembly of free-standing, one-particle thick films. When the average number of proteins per nanoparticle is lowered, the extent of self-assembly is limited to oligomeric particle clusters. Finally, we demonstrate that the aggregates are reversibly disassembled by an excess of one free protein. Our approach could be optimized for applications in biosensing, cell targeting, or functional nanomaterials engineering.

Modal engineering of Surface Plasmons in apertured Au Nanoprisms.

Crystalline gold nanoprisms of sub-micrometric size sustain high order plasmon modes in the visible and near infrared range that open a new realm for plasmon modal design, integrated coplanar devices and logic gates. In this article, we explore the tailoring of the surface plasmon local density of states (SP-LDOS) by embedding a single defect, namely a small hole, carved in the platelet by focused ion beam (FIB). The change in the SP-LDOS of the hybrid structure is monitored by two-photon luminescence (TPL) microscopy. The dependency of the two-dimensional optical field intensity maps on the linear polarization of the tightly focused femtosecond laser beam reveals the conditions for which the hole defect significantly affects the initial modes. A detailed numerical analysis of the spectral characteristics of the SP-LDOS based on the Green dyadic method clearly indicates that the hole size and location can be exploited to tune or remove selected SP modes.

Molecular decay rate near nonlocal plasmonic particles.

When the size of metal nanoparticles is smaller than typically 10 nm, their optical response becomes sensitive to both spatial dispersion and quantum size effects associated with the confinement of the conduction electrons inside the particle. In this Letter, we propose a nonlocal scheme to compute molecular decay rates near spherical nanoparticles which includes the electron-electron interactions through a simple model of electronic polarizabilities. The plasmonic particle is schematized by a dynamic dipolar polarizability α(NL)(ω), and the quantum system is characterized by a two-level system. In this scheme, the light matter interaction is described in terms of classical field susceptibilities. This theoretical framework could be extended to address the influence of nonlocality on the dynamics of quantum systems placed in the vicinity of nano-objects of arbitrary morphologies.

Multimodal plasmonics in fused colloidal networks.

Harnessing the optical properties of noble metals down to the nanometre scale is a key step towards fast and low-dissipative information processing. At the 10-nm length scale, metal crystallinity and patterning as well as probing of surface plasmon properties must be controlled with a challenging high level of precision. Here, we demonstrate that ultimate lateral confinement and delocalization of surface plasmon modes are simultaneously achieved in extended self-assembled networks comprising linear chains of partially fused gold nanoparticles. The spectral and spatial distributions of the surface plasmon modes associated with the colloidal superstructures are evidenced by performing monochromated electron energy-loss spectroscopy with a nanometre-sized electron probe. We prepare the metallic bead strings by electron-beam-induced interparticle fusion of nanoparticle networks. The fused superstructures retain the native morphology and crystallinity but develop very low-energy surface plasmon modes that are capable of supporting long-range and spectrally tunable propagation in nanoscale waveguides.

Tailoring and imaging the plasmonic local density of states in crystalline nanoprisms.

Surface plasmon (SP) technologies exploit the spectral and spatial properties of collective electronic oscillations in noble metals placed in an incident optical field. Yet the SP local density of states (LDOS), which rule the energy transducing phenomena between the SP and the electromagnetic field, is much less exploited. Here, we use two-photon luminescence (TPL) microscopy to reveal the SP-LDOS in thin single-crystalline triangular gold nanoprisms produced by a quantitative one-pot synthesis at room temperature. Variations of the polarization and the wavelength of the incident light redistribute the TPL intensity into two-dimensional plasmonic resonator patterns that are faithfully reproduced by theoretical simulations. We demonstrate that experimental TPL maps can be considered as the convolution of the SP-LDOS with the diffraction-limited Gaussian light beam. Finally, the SP modal distribution is tuned by the spatial coupling of nanoprisms, thus allowing a new modal design of plasmonic information processing devices.

Evaluating plasmonic transport in current-carrying silver nanowires.

Plasmonics is an emerging technology capable of simultaneously transporting a plasmonic signal and an electronic signal on the same information support. In this context, metal nanowires are especially desirable for realizing dense routing networks. A prerequisite to operate such shared nanowire-based platform relies on our ability to electrically contact individual metal nanowires and efficiently excite surface plasmon polaritons in this information support. In this article, we describe a protocol to bring electrical terminals to chemically-synthesized silver nanowires randomly distributed on a glass substrate. The positions of the nanowire ends with respect to predefined landmarks are precisely located using standard optical transmission microscopy before encapsulation in an electron-sensitive resist. Trenches representing the electrode layout are subsequently designed by electron-beam lithography. Metal electrodes are then fabricated by thermally evaporating a Cr/Au layer followed by a chemical lift-off. The contacted silver nanowires are finally transferred to a leakage radiation microscope for surface plasmon excitation and characterization. Surface plasmons are launched in the nanowires by focusing a near infrared laser beam on a diffraction-limited spot overlapping one nanowire extremity. For sufficiently large nanowires, the surface plasmon mode leaks into the glass substrate. This leakage radiation is readily detected, imaged, and analyzed in the different conjugate planes in leakage radiation microscopy. The electrical terminals do not affect the plasmon propagation. However, a current-induced morphological deterioration of the nanowire drastically degrades the flow of surface plasmons. The combination of surface plasmon leakage radiation microscopy with a simultaneous analysis of the nanowire electrical transport characteristics reveals the intrinsic limitations of such plasmonic circuitry.

Plasmonic nanoparticle networks for light and heat concentration.

Self-assembled plasmonic nanoparticle networks (PNN) composed of chains of 12 nm diameter crystalline gold nanoparticles exhibit a longitudinally coupled plasmon mode centered at 700 nm. We have exploited this longitudinal absorption band to efficiently confine light fields and concentrate heat sources in the close vicinity of these plasmonic chain networks. The mapping of the two phenomena on the same superstructures was performed by combining two-photon luminescence and fluorescence polarization anisotropy imaging techniques. Besides the light and heat concentration, we show experimentally that the planar spatial distribution of optical field intensity can be simply modulated by controlling the linear polarization of the incident optical excitation. On the contrary, the heat production, which is obtained here by exciting the structures within the optically transparent window of biological tissues, is evenly spread over the entire PNN. This contrasts with the usual case of localized heating in continuous nanowires, thus opening opportunities for these networks in light-induced hyperthermia applications. Furthermore, we propose a unified theoretical framework to account for both the nonlinear optical and thermal near-fields around PNN. The associated numerical simulations, based on a Green's function formalism, are in excellent agreement with the experimental images. This formalism therefore provides a versatile tool for the accurate engineering of optical and thermodynamical properties of complex plasmonic colloidal architectures.

Imaging symmetry-selected corner plasmon modes in penta-twinned crystalline Ag nanowires.

Using dual-plane leakage radiation microscopy, we investigate plasmon propagation in individual penta-twinned crystalline silver nanowires. By measuring the wavevector content of the light emitted in the substrate, we unambiguously determine the effective index and the losses of the mode propagating in these structures. The experimental results, in particular, the unexpectedly low effective index, reveal the direct influence of the nanowire crystallinity and pentagonal structure on the observed plasmon modes. By analogy with molecular orbitals of similar symmetry, the plasmon modes are also determined numerically in good agreement with the observed values. We further investigate the effect of wire geometry (length, diameter) on the effective index and propagation loss. Our results show that, beyond dissipation concerns, the morphological and structural control obtained in crystalline colloidal plasmonic nanostructures can be exploited to finely tune their optical properties.