All Publications

Yagi-Uda antennas are a key technology for efficiently transmitting information from point to point using radio waves. Since higher frequencies allow higher bandwidths and smaller footprints, a strong incentive exists to shrink Yagi-Uda antennas down to the optical regime. Here we demonstrate electrically-driven Yagi-Uda antennas for light with wavelength-scale footprints that exhibit large directionalities with forward-to-backward ratios of up to 9.1 dB. Light generation is achieved via antenna-enhanced inelastic tunneling of electrons over the antenna feed gap. We obtain reproducible tunnel gaps by means of feedback-controlled dielectrophoresis, which precisely places single surface-passivated gold nanoparticles in the antenna gap. The resulting antennas perform equivalent to radio-frequency antennas and combined with waveguiding layers even outperform RF designs. This work paves the way for optical on-chip data communication that is not restricted by Joule heating but also for advanced light management in nanoscale sensing and metrology as well as light emitting devices.

We use mono-crystalline gold platelets with ultra-smooth surfaces and superior plasmonic properties to investigate the formation of interference patterns caused by surface plasmon polaritons (SPPs) with scattering-type scanning near-field microscopy at 521 and 633 nm. By applying a Fourier analysis approach, we can identify and separate several signal channels related to SPPs launched and scattered by the atomic force microscopy tip and the edges of the platelet. Especially at the excitation wavelength of 633 nm, we can isolate a region in the center of the platelets where we find only contributions of SPPs which are launched by the tip and reflected at the edges. These signatures are used to determine the SPP wavelength of λSPP = 606 nm in good agreement with theoretical predictions. Furthermore, we were still able to measure SPP signals after 20 µm propagation, which demonstrates impressively the superior plasmonic quality of these mono-crystalline gold platelets.

We describe a setup for time-resolved photoemission electron microscopy with aberration correction enabling 3 nm spatial resolution and sub-20 fs temporal resolution. The latter is realized by our development of a widely tunable (215–970 nm) noncollinear optical parametric amplifier (NOPA) at 1 MHz repetition rate. We discuss several exemplary applications. Efficient photoemission from plasmonic Au nanoresonators is investigated with phase-coherent pulse pairs from an actively stabilized interferometer. More complex excitation fields are created with a liquid-crystal-based pulse shaper enabling amplitude and phase shaping of NOPA pulses with spectral components from 600 to 800 nm. With this system we demonstrate spectroscopy within a single plasmonic nanoslit resonator by spectral amplitude shaping and investigate the local field dynamics with coherent two-dimensional (2D) spectroscopy at the nanometer length scale (“2D nanoscopy”). We show that the local response varies across a distance as small as 33 nm in our sample. Further, we report two-color pump–probe experiments using two independent NOPA beamlines. We extract local variations of the excited-state dynamics of a monolayered 2D material (WSe2) that we correlate with low-energy electron microscopy (LEEM) and reflectivity measurements. Finally, we demonstrate the in situ sample preparation capabilities for organic thin films and their characterization via spatially resolved electron diffraction and dark-field LEEM.

The optimization of nonlinear optical processes on the nanoscale is a crucial step for the integration of complex functionalities into compact photonic devices and metasurfaces. In such systems, photon upconversion can be achieved with higher efficiencies via third-order processes, such as third-harmonic generation (THG), thanks to the resonantly enhanced volume currents. Conversely, second-order processes, such as second-harmonic generation (SHG), are often inhibited by the symmetry of metal lattices and of common nanoantenna geometries. SHG and THG processes in plasmonic nanostructures are generally treated independently because they typically represent small perturbations in the light–matter interaction mechanisms. In this work, we demonstrate that this paradigm does not hold for plasmon-enhanced nonlinear optics by providing evidence of a sum-frequency generation (SFG) process seeded by SHG, which sizably contributes to the overall THG yield. We address this mechanism by unveiling a characteristic fingerprint in the polarization state of the THG emission from gold noncentrosymmetric nanoantennas, which directly reflects the asymmetric distribution of second-harmonic fields within the structure and does not depend on the model one employs to describe photon upconversion. We suggest that such cascaded processes may also appear for structures that exhibit only moderate SHG yields. The presence of this peculiar mechanism in THG from plasmonic nanoantennas at telecommunication wavelengths allows us to gain further insight into the physics of plasmon-enhanced nonlinear optical processes. This could be crucial in the realization of nanoscale elements for photon conversion and manipulation operating at room temperature.

Placing a plasmonic nanorod near the termination of a plasmonic nanowire dramatically changes the reflection of the wire's guided mode. By carefully choosing the length of the nanorod, the reflectivity at the wire termination nearly vanishes due to destructive interference between the directly reflected wire mode and the infinite sum of the partial transmissions back into the wire of the reflected modes inside the nanorod. We show that this near-zero reflection condition corresponds to the so far overlooked nonbonding resonance which corresponds to a minimal coupling condition with extreme sensitivity to any changes in the nanorod's local environment. We explicitly quantify the sensitivity of the nonbonding condition towards small local and global perturbations of the refractive index and outline a method to exploit the nonbonding condition for near-field ultrasensing.

Plasmonic resonators can be designed to support spectrally well-separated discrete modes. The associated characteristic spatial patterns of intense electromagnetic hot-spots can be exploited to enhance light–matter interaction. Here, we study the local field dynamics of individual hot-spots within a nanoslit resonator by detecting characteristic changes of the photoelectron emission signal on a scale of ∼12 nm using time-resolved photoemission electron microscopy (TR-PEEM) and by excitation with the output from a 20 fs, 1 MHz noncollinear optical parametric amplifier (NOPA). Surprisingly, we detect apparent spatial variations of the Q-factor and resonance frequency that are commonly considered to be global properties for a single mode. By using the concept of quasinormal modes we explain these local differences by crosstalk of adjacent resonator modes. Our findings are important in view of time-domain studies of plasmon-mediated strong light–matter coupling at ambient conditions.

Gold nanostructures have important applications in nanoelectronics, nano-optics, and in precision metrology due to their intriguing optoelectronic properties. These properties are governed by the bulk band structure but to some extent are tunable via geometrical resonances. Here we show that the band structure of gold itself exhibits significant size-dependent changes already for mesoscopic critical dimensions below 30 nm. To suppress the effects of geometrical resonances and grain boundaries, we prepared atomically flat ultrathin films of various thicknesses by utilizing large chemically grown single-crystalline gold platelets. We experimentally probe thickness-dependent changes of the band structure by means of two-photon photoluminescence and observe a surprising 100-fold increase of the nonlinear signal when the gold film thickness is reduced below 30 nm allowing us to optically resolve single-unit-cell steps. The effect is well explained by density functional calculations of the thickness-dependent 2D band structure of gold.

The photon spin is an important resource for quantum information processing as is the electron spin in spintronics. However, for subwavelength confined optical excitations, polarization as a global property of a mode cannot be defined. Here, we show that any polarization state of a plane-wave photon can reversibly be mapped to a pseudospin embodied by the two fundamental modes of a subwavelength plasmonic two-wire transmission line. We design a device in which this pseudospin evolves in a well-defined fashion throughout the device reminiscent of the evolution of photon polarization in a birefringent medium and the behavior of electron spins in the channel of a spin field-effect transistor. The significance of this pseudospin is enriched by the fact that it is subject to spin–orbit locking. Combined with optically active materials to exert external control over the pseudospin precession, our findings could enable spin-optical transistors, that is, the routing and processing of quantum information with light on a subwavelength scale.

We observe strongly dissimilar scattering from the two types of sidewall configurations (here referred to as “edges”) in hexagonal quasi-monocrystalline gold flakes with thicknesses around 1 micron. As the origin of the phenomena, we identify the interference between a direct, quasi-specular scattering and an indirect scattering process involving an intermediate surface-plasmon state. The dissimilarity between the two types of edges is a direct consequence of the three-fold symmetry around the [111]-axis and the intrinsic chirality of a face-centered cubic lattice. We propose that this effect can be potentially used to estimate dielectric function of the monocrystalline gold.

Helium ion milling of chemically-synthesized micron-sized gold flakes is performed to fabricate ultra-narrow nanoslit cavities with a varying length and width down to 5 nm. Their plasmon resonances are characterized by one-photon photoluminescence spectroscopy. The combination of fabrication based on single-crystalline gold and resonant modes with low radiative losses leads to remarkably high quality factors of up to 24. Multiple Fabry–Pérot-type resonances in the visible/near infrared spectral range are observed due to the achieved narrow slit widths and the resulting short effective wavelengths of nanoslit plasmons. These features make nanoslit cavities attractive for a range of applications such as surface-enhanced spectroscopy, ultrafast nano-optics and strong light–matter coupling.

In the vicinity of metallic nanostructures, absorption and emission rates of optical emitters can be modulated by several orders of magnitude. Control of such near-field light–matter interaction is essential for applications in biosensing, light harvesting and quantum communication and requires precise mapping of optical near-field interactions, for which single-emitter probes are promising candidates. However, currently available techniques are limited in terms of throughput, resolution and/or non-invasiveness. Here, we present an approach for the parallel mapping of optical near-field interactions with a resolution of textless5 nm using surface-bound motor proteins to transport microtubules carrying single emitters (quantum dots). The deterministic motion of the quantum dots allows for the interpolation of their tracked positions, resulting in an increased spatial resolution and a suppression of localization artefacts. We apply this method to map the near-field distribution of nanoslits engraved into gold layers and find an excellent agreement with finite-difference time-domain simulations. Our technique can be readily applied to a variety of surfaces for scalable, nanometre-resolved and artefact-free near-field mapping using conventional wide-field microscopes.

Creating sub-micron hotspots for applications such as heat-assisted magnetic recording (HAMR) is a challenging task. The most common approach relies on a surface-plasmon resonator (SPR), whose design dictates the size of the hotspot to always be larger than its critical dimension. Here, we present an approach which circumvents known geometrica restrictions by resorting to electric field confinement via excitation of a gap-mode (GM) between a comparatively large Gold (Au) nano-sphere (radius of 100 nm) and the magnetic medium in a grazing-incidence configuration. Operating a λ=785 nm laser, sub-200 nm hot spots have been generated and successfully used for GM-assisted magnetic switching on commercial CoCrPt perpendicular magnetic recording media at laser powers and pulse durations comparable to SPR-based HAMR. Lumerical electric field modelling confirmed that operating in the near-infrared regime presents a suitable working point where most of the light's energy is deposited in the magnetic layer, rather than in the nano-particle. Further, modelling is used for predicting the limits of our method which, in theory, can yield sub-30 nm hotspots for Au nano-sphere radii of 25–50 nm for efficient heating of FePt recording media with a gap of 5 nm.

Strong coupling and the resultant mixing of light and matter states is an important asset for future quantum technologies. We demonstrate deterministic room temperature strong coupling of a mesoscopic colloidal quantum dot to a plasmonic nanoresonator at the apex of a scanning probe. Enormous Rabi splittings of up to 110 meV are accomplished by nanometer-precise positioning of the quantum dot with respect to the nanoresonator probe. We find that, in addition to a small mode volume of the nanoresonator, collective coherent coupling of quantum dot band-edge states and near-field proximity interaction are vital ingredients for the realization of near-field strong coupling of mesoscopic quantum dots. The broadband nature of the interaction paves the road toward ultrafast coherent manipulation of the coupled quantum dot-plasmon system under ambient conditions.

We describe the wet-chemical synthesis of high-aspect-ratio single-crystalline gold platelets with thicknesses down to 20 nm and edge lengths up to 0.2 mm. By employing statistical analysis of a large number of platelets, we investigate the effect of temperature on the growth velocities of the top and side facets for constant concentrations of the three common ingredients: ethylene glycol, chloroauric acid, and water. We further show that by varying the chemical environment during growth, the ratio between the growth velocities can be adjusted, and thus thickness and lateral size can be tuned independently. Very large but ultrathin single-crystalline gold platelets represent an important starting material for top-down nanofabrication and may also find applications as transparent conducting substrates as well as substrates for high-end scanning probe and electron microscopy.

Antennas play a key role in today’s wireless communication networks and it would be hugely beneficial to extent their use into the optical regime. However, classical signal generators do not work at those frequencies and therefore new concepts are needed. Here, we demonstrate how to electrically drive an optical nanoantenna using an atomic-scale feed gap provided by a gold-particle pushed into a precisely tailored interstice between two antenna arms. Upon applying a voltage, inelastic electron tunneling leads to current fluctuations in the optical regime and, hence, light emission. We show how the antennas spectrally shape the emission, how the exact particle position influences these properties and how to increase the directivity via Yagi-Uda arrangements or plasmonic waveguides structures in order to make electricallydriven optical nanoantennas more suitable for on-chip data communication.

The validity of Kirchhoff’s laws in plasmonic nanocircuitry is investigated by studying a junction of plasmonic two-wire transmission lines. We find that Kirchhoff’s laws are valid for sufficiently small values of a phenomenological parameter κ relating the geometrical parameters of the transmission line with the effective wavelength of the guided mode. Beyond such regime, for large values of the phenomenological parameter, increasing deviations occur and the equivalent impedance description (Kirchhoff’s laws) can only provide rough, but nevertheless useful, guidelines for the design of more complex plasmonic circuitry. As an example we investigate a system composed of a two-wire transmission line and a nanoantenna as the load. By addition of a parallel stub designed according to Kirchhoff’s laws we achieve maximum signal transfer to the nanoantenna.

The emission rate of a point dipole can be strongly increased in the presence of a well-designed optical antenna. Yet, optical antenna design is largely based on radio-frequency rules, ignoring, e.g., Ohmic losses and non-negligible field penetration in metals at optical frequencies. Here, we combine reciprocity and Poynting’s theorem to derive a set of optical-frequency antenna design rules for benchmarking and optimizing the performance of optical antennas driven by single quantum emitters. Based on these findings a novel plasmonic cavity antenna design is presented exhibiting a considerably improved performance compared to a reference two-wire antenna. Our work will be useful for the design of high-performance optical antennas and nanoresonators for diverse applications ranging from quantum optics to antenna-enhanced single-emitter spectroscopy and sensing.

Radiationless energy transfer is at the core of diverse phenomena, such as light harvesting in photosynthesis, energy-transfer-based microspectroscopies, nanoscale quantum entanglement and photonic-mode hybridization. Typically, the transfer is efficient only for separations that are much shorter than the diffraction limit. This hampers its application in optical communication and quantum information processing, which require spatially selective addressing. Here, we demonstrate highly efficient radiationless coherent energy transfer over a distance of twice the excitation wavelength by combining localized and delocalized plasmonic modes. Analogous to the Tavis–Cummings model, two whispering-gallery-mode antennas placed in the foci of an elliptical plasmonic cavity fabricated from single-crystal gold plates act as a pair of oscillators coupled to a common cavity mode. Time-resolved two-photon photoemission electron microscopy (TR 2P-PEEM) reveals an ultrafast long-range periodic energy transfer in accordance with the simulations. Our observations open perspectives for the optimization and tailoring of mesoscopic energy transfer and long-range quantum emitter coupling.

Quantum photonics holds great promise for future technologies such as secure communication, quantum computation, quantum simulation, and quantum metrology. An outstanding challenge for quantum photonics is to develop scalable miniature circuits that integrate single-photon sources, linear optical components, and detectors on a chip. Plasmonic nanocircuits will play essential roles in such developments. However, for quantum plasmonic circuits, integration of stable, bright, and narrow-band single photon sources in the structure has so far not been reported. Here we present a plasmonic nanocircuit driven by a self-assembled GaAs quantum dot. Through a planar dielectric-plasmonic hybrid waveguide, the quantum dot efficiently excites narrow-band single plasmons that are guided in a two-wire transmission line until they are converted into single photons by an optical antenna. Our work demonstrates the feasibility of fully on-chip plasmonic nanocircuits for quantum optical applications.

Exact quantitative understanding of plasmon propagation along nanowires is mandatory for designing and creating functional devices. Here we investigate plasmon transmission through top-down-fabricated monocrystalline gold nanowires on a glass substrate. We show that the transmission through finite-length nanowires can be described by Fabry–Pérot oscillations that beat with free-space propagating light launched at the incoupling end. Using an extended Fabry–Pérot model, experimental and simulated length-dependent transmission signals agree quantitatively with a fully analytical model.

We demonstrate the feasibility of a thermal imprint technology capable of structuring organic thin films with liquid crystalline properties forming feature sizes on a several micrometer scale. The imprint technique can directly be applied onto a variety of substrates including dielectric mirrors. The so fabricated three-dimensional microcavities have lateral extensions up to 20 μm and heights between 1 and 5 μm. Exemplarily, pillar microcavities were produced wherein three-dimensional photonic confinement is observed by the formation of 0D cavity mode patterns. The imprint technique further favors the formation of hemispherical pillar geometries rather than cylindrical pillars, resulting in equidistant mode spacings of transversal cavity modes.

Nanoantennas can tailor light-matter interaction for optical communication, sensing, and spectroscopy. Their design is inspired by radio-frequency rules which partly break down at optical frequencies. Here we find unexpected nanoantenna designs exhibiting strong light localization and enhancement by using a general and scalable evolutionary algorithm based on FDTD simulations that also accounts for geometrical fabrication constraints. The resulting nanoantennas are "printed" directly by focused-ion beam milling and their fitness ranking is validated experimentally by two-photon photoluminescence. We find the best antennas' operation principle deviating from that of classical radio wave-inspired designs. Our work sets the stage for a widespread application of evolutionary optimization in nano photonics.

Heat-assisted magnetic recording (HAMR) is often considered the next major step in the storage industry: it is predicted to increase the storage capacity, the read/write speed and the data lifetime of future hard disk drives. However, despite more than a decade of development work, the reliability is still a prime concern. Featuring an inherently fragile surface-plasmon resonator as a highly localized heat source, as part of a near-field transducer (NFT), the current industry concepts still fail to deliver drives with sufficient lifetime. This study presents a method to aid conventional NFT-designs by additional grazing-incidence laser illumination, which may open an alternative route to high-durability HAMR. Magnetic switching is demonstrated on consumer-grade CoCrPt perpendicular magnetic recording media using a green and a near-infrared diode laser. Sub-500 nm magnetic features are written in the absence of a NFT in a moderate bias field of only μ0H = 0.3 T with individual laser pulses of 40 mW power and 50 ns duration with a laser spot size of 3 μm (short axis) at the sample surface – six times larger than the magnetic features. Herein, the presence of a nanoscopic object, i.e., the tip of an atomic force microscope in the focus of the laser at the sample surface, has no impact on the recorded magnetic features – thus suggesting full compatibility with NFT-HAMR.

The design of noble-metal plasmonic devices and nanocircuitry requires a fundamental understanding and control of the interference of plasmonic modes. Here we report the first visualization of the propagation and interference of guided modes in a showcase plasmonic nanocircuit using normal-incidence nonlinear two-photon photoemission electron microscopy (PEEM). We demonstrate that in contrast to the commonly used grazing-incidence illumination scheme, normal-incidence PEEM provides a direct image of the structure’s near-field intensity distribution due to the absence of beating patterns and despite the transverse character of the plasmonic modes. Based on a simple heuristic numerical model for the photoemission yield, we are able to model all experimental findings if global plane wave illumination and coupling to multiple input/output ports, and the resulting interference effects are accounted for.

The two-photon photopolymerization of resins by focused laser light in principle enables the fabrication of structures with details below the diffraction limit. However, the method can be highly susceptible to aberrations, which hinders the fabrication of structures that are larger than, e.g., the working distance of the microscope objective. Here, two-photon polymerization is extended to the fabrication of macroscopic structures by making use of medium numerical-aperture microscope objectives. By introducing a substrate holder movable in the axial direction it is possible to keep the focusing conditions constant and to fabricate very large structures with heights that are not limited by the working distance of the objective. Moreover, the constant focusing conditions enable us to quantify spherical aberrations by experimental mapping of the optical point-spread function, which manifests itself in the shape of singe photo-polymerized voxels. By monitoring such shapes it is possible to minimize aberrations. Effective aberration control enables us to fabricate large but detailed biomedical scaffolds with interconnected pores, e.g., in the shape of a human stirrup bone.

The field enhancement of individual cross-shaped nanoantennas for normal incident light has been measured by the relative photoemission yield using a photoemission electron microscope. We not only measured the electron yield in dependence on the intensity of infrared light (800 nm, 100 fs), but also the polarization dependence. In the normal incidence geometry, the electrical field vector of the illuminating light lies in the surface plane of the sample, independent of the polarization state. Strong yield variations due to an out-of-plane field component as well as changes in the polarization state described by the Fresnel laws are avoided. The electron yield is related to the near-field enhancement as a function of the polarization state of the incident light. The polarization dependence is well explained by numerical simulations.

Coupling mechanical degrees of freedom with plasmonic resonances has potential applications in optomechanics, sensing, and active plasmonics. Here we demonstrate a suspended two-wire plasmonic nanoantenna acting like a nanoelectrometer. The antenna wires are supported and electrically connected via thin leads without disturbing the antenna resonance. As a voltage is applied, equal charges are induced on both antenna wires. The resulting equilibrium between the repulsive Coulomb force and the restoring elastic bending force enables us to precisely control the gap size. As a result the resonance wavelength and the field enhancement of the suspended optical nanoantenna can be reversibly tuned. Our experiments highlight the potential to realize large bandwidth optical nanoelectromechanical systems.

The nonlinear refractive index of plasmonic materials may be used to obtain nonlinear functionality, e.g., power-dependent switching. Here, we investigate the nonlinear refractive index of single-crystalline gold in thin layers and nanostructures on dielectric substrates. In a first step, we implement a z-scan setup to investigate ~100-µm-sized thin-film samples. We determine the nonlinear refractive index of fused silica, n2(SiO2) = 2.9 × 10^(−20) m^2/W, in agreement with literature values. Subsequent z-scan measurements of single-crystalline gold films reveal a damage threshold of 0.22 TW/cm^2 and approximate upper limits of the real and imaginary parts of the nonlinear refractive index, |n2′(Au)| < 1.2 × 10^(−16) m^2/W and |n2″(Au)| < 0.6 × 10^(−16) m^2/W, respectively. To further determine possible effects of a nonlinear refractive index in plasmonic circuitry, interferometry is proposed as a phase-sensitive probe. In corresponding nanostructures, relative phase changes between two propagating near-field modes are converted to amplitude changes by mode interference. Power-dependent experiments using sub-10-fs near-infrared pulses and diffraction-limited resolution (NA = 1.4) reveal linear behavior up to the damage threshold (0.23 times relative to that of a solid single-crystalline gold film). An upper limit for the nonlinear power-dependent phase change between two propagating near-field modes is determined to Δφ < 0.07 rad.

Single femtosecond optical laser pulses, of sufficient intensity, are demonstrated to reverse magnetization in a process known as all-optical switching. Gold two-wire antennas are placed on the all-optical switching film TbFeCo. These structures are resonant with the optical field, and they create a field enhancement in the near-field which confines the area where optical switching can occur. The magnetic switching that occurs around and below the antenna is imaged using resonant X-ray holography and magnetic circular dichroism. The results not only show the feasibility of controllable switching with antenna assistance but also demonstrate the highly inhomogeneous nature of the switching process, which is attributed to the process depending on the material’s heterogeneity.

The demand for using nanostructures fabricated by focused ion beam (FIB) on delicate substrates or as building blocks for complex devices motivates the development of protocols that allow FIB-fabricated nanostructures to be transferred from the original substrate to the desired target. However, transfer of FIB-fabricated nanostructures is severely hindered by FIB-induced welding of structure and substrate. Here we present two (ex and in situ) transfer methods for FIB-fabricated nanostructures based on a silica–gold bilayer evaporated onto a bulk substrate. Utilizing the poor adhesion between silica and gold, the nanostructures can be mechanically separated from the bulk substrate. For the ex situ transfer, a spin-coated poly(methyl methacrylate) film is used to carry the nanostructures so that the bilayer can be etched away after being peeled off. For the in situ transfer, using a micro-manipulator inside the FIB machine, a cut-out piece of silica on which a nanostructure has been fabricated is peeled off from the bulk substrate and thus carries the nanostructure to a target substrate. We demonstrate the performance of both methods by transferring plasmonic nano-antennas fabricated from single-crystalline gold flakes by FIB milling to a silicon wafer and to a scanning probe tip.

Unlike radiowave antennas, so far optical nanoantennas cannot be fed by electrical generators. Instead, they are driven by light or indirectly via excited discrete states in active materials in their vicinity. Here we demonstrate the direct electrical driving of an in-plane optical antenna by the broadband quantum-shot noise of electrons tunnelling across its feed gap. The spectrum of the emitted photons is determined by the antenna geometry and can be tuned via the applied voltage. Moreover, the direction and polarization of the light emission are controlled by the antenna resonance, which also improves the external quantum efficiency by up to two orders of magnitude. The one-material planar design offers facile integration of electrical and optical circuits and thus represents a new paradigm for interfacing electrons and photons at the nanometre scale, for example for on-chip wireless communication and highly configurable electrically driven subwavelength photon sources.

Chemically synthesized single-crystalline gold microplates have been attracting increasing interest because of their potential as high-quality gold films for nanotechnology. We present the growth of tens of nanometers thick and tens of micrometers large single-crystalline gold plates directly on solid substrates by solution-phase synthesis. Compared to microplates deposited on substrates from dispersion phase, substrate-grown plates exhibit significantly higher quality by avoiding severe small-particle contamination and aggregation. Substrate-grown gold plates also open new perspectives to study the growth mechanism via step-growth and observation cycles of a large number of individual plates. Growth models are proposed to interpret the evolution of thickness, area and shape of the plates. It is found that the plate surface remains smooth after regrowth, implying the applicability of regrowth for producing giant plates as well as unique single-crystalline nano-structures.

Using a combination of photoemission electron microscopy and numerical simulations, we investigated the angular moment transfer in strongly enhanced optical near-fields of artificially fabricated optical antennas. The polarization dependence of the optical near-field enhancement has been measured in a maximum symmetric geometry, i.e., excitation by a normal incident planar wave. Finite-difference time-domain simulations for the realistic antenna geometries as determined by high-resolution electron microscopy reveal a very good agreement with experimental data. The agreement confirms that the geometrical asymmetries and inhomogeneities due to the nanoscale fabrication process preserve the circular polarization in the gap regions with strong near-field enhancement.

Boosting nonlinear frequency conversion in extremely confined volumes remains a challenge in nano-optics research, but can enable applications in nanomedicine, photocatalysis and background-free biosensing. To obtain brighter nonlinear nanoscale sources, approaches that enhance the electromagnetic field intensity and counter the lack of phase matching in nanoplasmonic systems are often employed. However, the high degree of symmetry in the crystalline structure of plasmonic materials (metals in particular) and in nanoantenna designs strongly quenches second harmonic generation. Here, we describe doubly-resonant single-crystalline gold nanostructures with no axial symmetry displaying spatial mode overlap at both the excitation and second harmonic wavelengths. The combination of these features allows the attainment of a nonlinear coefficient for second harmonic generation of ∼5 × 10\textasciicircum(–10) W\textasciicircum(–1), enabling a second harmonic photon yield higher than 3 × 10textasciicircum6 photons per second. Theoretical estimations point toward the use of our nonlinear plasmonic nanoantennas as efficient platforms for label-free molecular sensing.

We experimentally investigate the smallest germanium waveguide cavity resonators on silicon that can be designed to work around 1.55 μm wavelength and observe an almost 30-fold enhancement in the collected spontaneous emission per unit volume when compared to a continuous germanium film of the same thickness. The enhancement is due to an effective combination of (i) excitation enhancement at the pump wavelength, (ii) emission enhancement (Purcell effect) at the emission wavelength, and (iii) effective beaming by the nanoresonators, which act as optical antennas to enhance the radiation efficiency. Our results set a basis for the understanding and engineering of light emission based on subwavelength, CMOS-compatible nanostructures operating at telecommunication wavelengths.

We describe a setup consisting of a 4f pulse shaper and a microscope with a high-NA objective lens and discuss the aspects most relevant for an undistorted spatiotemporal profile of the focused beam. We demonstrate shaper-assisted pulse compression in focus to a sub-10-fs duration using phase-resolved interferometric spectral modulation (PRISM). We introduce a nanostructure-based method for sub-diffraction spatiotemporal characterization of strongly focused pulses. The distortions caused by optical aberrations and space--time coupling from the shaper can be reduced by careful setup design and alignment to about 10 nm in space and 1 fs in time.

The integration of lab-on-a-chip technologies with single-molecule detection techniques may enable new applications in analytical chemistry, biotechnology, and medicine. We describe a method based on the reciprocity theorem of electromagnetic theory to determine and optimize the detection efficiency of photons emitted by single quantum emitters through truncated dielectric waveguides of arbitrary shape positioned in their proximity. We demonstrate experimentally that detection of single quantum emitters via such waveguides is possible, confirming the predicted behavior of the detection efficiency. Our findings blaze the trail towards efficient lensless single-emitter detection compatible with large-scale optofluidic integration.

The miniaturization of optical devices is a prerequisite for broadband data-processing technology to compete with cutting-edge nanoelectronic circuits. For these future nano-optical circuits, controlling the spatial and temporal evolution of surface plasmons, i.e., propagating optical near fields at metal-insulator interfaces, is a key feature. Here, we design, optimize, and fabricate a nanoscale directional coupler with one input and two output ports, a device that is an essential element of nano-optical circuits. The directional coupler is based on a two-wire transmission line supporting two plasmonic eigenmodes that can be selectively excited. By manipulating the input polarization of ultrashort pulses and pulse pairs and by characterizing the light emitted from both output ports, we demonstrate open-loop ultrafast spatial and spatiotemporal coherent control of plasmon propagation. Because of the intuitive and optimized design, which exploits a controlled near-field interference mechanism, varying the linear input polarization is enough to switch between both output ports of the nanoscale directional coupler. Since we exploit the interference of a finite spectrum of eigenmodes, our experiments represent a very intuitive classical analogue to quantum control in molecules.

We experimentally demonstrate synthesis and in situ analysis of multimode plasmonic excitations in two-wire transmission lines supporting a symmetric and an antisymmetric eigenmode. To this end we irradiate an incoupling antenna with a diffraction-limited excitation spot exploiting a polarization- and position-dependent excitation efficiency. Modal analysis is performed by recording the far-field emission of two mode-specific spatially separated emission spots at the far end of the transmission line. To illustrate the power of the approach we selectively determine the group velocities of symmetric and antisymmetric contributions of a multimode ultrafast plasmon pulse.

In the presence of matter, there is no fundamental limit preventing confinement of visible light even down to atomic scales. Achieving such confinement and the corresponding resonant intensity enhancement inevitably requires simultaneous control over atomic-scale details of material structures and over the optical modes that such structures support. By means of self-assembly we have obtained side-by-side aligned gold nanorod dimers with robust atomically defined gaps reaching below 0.5 nm. The existence of atomically confined light fields in these gaps is demonstrated by observing extreme Coulomb splitting of corresponding symmetric and antisymmetric dimer eigenmodes of more than 800 meV in white-light scattering experiments. Our results open new perspectives for atomically resolved spectroscopic imaging, deeply nonlinear optics, ultrasensing, cavity optomechanics, as well as for the realization of novel quantum-optical devices.

The design of nanoantennas has so far been mainly inspired by radio-frequency technology. However, the material properties and experimental settings need to be reconsidered at optical frequencies, which would entail the need for alternative optimal antenna designs. Here we subject a checkerboard-type, initially random array of gold cubes to evolutionary optimization. To illustrate the power of the approach, we demonstrate that by optimizing the near-field intensity enhancement, the evolutionary algorithm finds a new antenna geometry, essentially a split-ring–two-wire antenna hybrid that surpasses by far the performance of a conventional gap antenna by shifting the n=1 split-ring resonance into the optical regime.

Electrically connected resonant optical antennas hold promise for the realization of highly efficient nanoscale electro-plasmonic devices that rely on a combination of electric fields and local near-field intensity enhancement. Here we demonstrate the feasibility of such a concept by attaching leads to the arms of a two-wire antenna at positions of minimal near-field intensity with negligible influence on the antenna resonance. White-light scattering experiments in accordance with simulations show that the optical tunability of connected antennas is fully retained. Analysis of the electric properties demonstrates that in the antenna gaps direct current (DC) electric fields of 108 V/m can consistently be achieved and maintained over extended periods of time without noticeable damage.

Plasmonic modes supported by noble-metal nanostructures offer strong subwavelength electric-field confinement and promise the realization of nanometer-scale integrated optical circuits with well-defined functionality. In order to measure the spectral and spatial response functions of such plasmonic elements, we combine a confocal microscope setup with spectral interferometry detection. The setup, data acquisition, and data evaluation are discussed in detail by means of exemplary experiments involving propagating plasmons transmitted through silver nanowires. By considering and experimentally calibrating any setup-inherent signal delay with an accuracy of 1 fs, we are able to extract correct timing information of propagating plasmons. The method can be applied, e.g., to determine the dispersion and group velocity of propagating plasmons in nanostructures, and can be extended towards the investigation of nonlinear phenomena.

Two-pulse correlation is employed to investigate the temporal dynamics of both two-photon photoluminescence (2PPL) and four-photon photoluminescence (4PPL) in resonant and nonresonant nanoantennas excited at a wavelength of 800 nm. Both 2PPL and 4PPL data are consistent with the same two-step model already established for 2PPL, implying that the first excitation step in 4PPL is a three-photon sp → sp direct interband transition. Considering energy and parity conservation, we also explain why 4PPL behavior is favored over, for example, three- and five-photon photoluminescence in the power range below the damage threshold of our antennas. Since sizable 4PPL requires larger peak intensities of the local field, we are able to select either 2PPL or 4PPL in the same gold nanoantennas by choosing a suitable laser pulse duration. We thus provide a first consistent model for the understanding of multiphoton photoluminescence generation in gold nanoantennas, opening new perspectives for applications ranging from the characterization of plasmonic resonances to biomedical imaging.

Two-photon fluorescence scanning confocal microscopy sensitive to circular dichroism with a diffraction-limited resolution well below 500 nm is demonstrated. With this method, the spatial variation of the circular dichroism of thermally annealed chiral polyfluorene thin films has been imaged. We observed circular dichroism associated with submicrometer-sized domains showing helicoidally twisted macromolecular organization. Domains with opposite chiroptical properties, corresponding to left- or right-handed molecular organization, coexist in the film. Our results are consistent with those obtained by one-photon imaging and illustrate the potential of two-photon imaging for use in studying helical macromolecular organization.

Nanoantennas for visible and infrared radiation can strongly enhance the interaction of light with nanoscale matter by their ability to efficiently link propagating and spatially localized optical fields. This ability unlocks an enormous potential for applications ranging from nanoscale optical microscopy and spectroscopy over solar energy conversion, integrated optical nanocircuitry, opto-electronics and density-of-states engineering to ultra-sensing as well as enhancement of optical nonlinearities. Here we review the current understanding of metallic optical antennas based on the background of both well-developed radiowave antenna engineering and plasmonics. In particular, we discuss the role of plasmonic resonances on the performance of nanoantennas and address the influence of geometrical parameters imposed by nanofabrication. Finally, we give a brief account of the current status of the field and the major established and emerging lines of investigation in this vivid area of research.

Spectral interferometry is employed to fully characterize amplitude and phase of propagating plasmons that are transmitted through silver nanowires in the form of ultrashort pulses. For nanowire diameters below 100 nm, the plasmon group velocity is found to decrease drastically in accordance with the theory of adiabatic focusing. Furthermore, the dependence of the plasmon group velocity on the local nanowire environment is demonstrated. Our findings are of relevance for the design and implementation of nanoplasmonic signal processing and in view of coherent control applications.

Thermally annealed chiral polyfluorene films are studied by circular differential optical microscopy. We observe the presence of micrometer-sized domains displaying circular dichroism of opposite sign. Our findings suggest the spontaneous occurrence of left- and right-handed cholesterically ordered domains from an enantiopure precursor. The role of enantiopure stereo centers in the side chains of the polymer is to lower the energy of the left-handed cholesteric domains with respect to the right-handed ones.

We explore the possibility to control the polarization state of light confined into sub-diffraction volumes by means of plasmonic optical antennas. To this aim, we describe a resonant cross antenna, constituted of two perpendicular two-wire antennas sharing the same gap, which is able to maintain the polarization state in the plane of the antenna. We also discuss how, by proper tuning of the arm length in a slightly off-resonance cross antenna, it is possible to effectively realize a nanoscale quarter-waveplate antenna. We present experimental results for the preparation of individual cross antennas by means of focused ion beam milling starting from single-crystalline Au microflakes, and finally show preliminary characterization results based on two-photon photoluminescence confocal imaging with linearly-polarized light.

Deep subwavelength integration of high-definition plasmonic nanostructures is of key importance in the development of future optical nanocircuitry for high-speed communication, quantum computation and lab-on-a-chip applications. To date, the experimental realization of proposed extended plasmonic networks consisting of multiple functional elements remains challenging, mainly because of the multi-crystallinity of commonly used thermally evaporated gold layers. This can produce structural imperfections in individual circuit elements that drastically reduce the yield of functional integrated nanocircuits. In this paper we demonstrate the use of large (\textgreater100 μm2) but thin (\textless80 nm) chemically grown single-crystalline gold flakes that, after immobilization, serve as an ideal basis for focused ion beam milling and other top-down nanofabrication techniques on any desired substrate. Using this methodology we obtain high-definition ultrasmooth gold nanostructures with superior optical properties and reproducible nano-sized features over micrometre-length scales. Our approach provides a possible solution to overcome the current fabrication bottleneck and realize high-definition plasmonic nanocircuitry.

The applicability of single-molecule fluorescence assays in liquids is limited by diffusion to concentrations in the low picomolar range. Here, we demonstrate quantitative single-molecule detection at attomolar concentrations within 1 min by excitation and detection of fluorescence through a single-mode optical fiber in presence of turbulent flow. The combination of high detectability and short measurement times promises applications in ultrasensitive assays, sensors, and point-of-care medical diagnostics.

The number of eigenmodes in plasmonic nanostructures increases with complexity due to mode hybridization, raising the need for efficient mode characterization and selection. Here we experimentally demonstrate direct imaging and selective excitation of the “bonding” and “antibonding” plasmon mode in symmetric dipole nanoantennas using confocal two-photon photoluminescence mapping. Excitation of a high-quality-factor antibonding resonance manifests itself as a two-lobed pattern instead of the single spot observed for the broad “bonding” resonance in accordance with numerical simulations. The two-lobed pattern is observed due to the fact that excitation of the antibonding mode is forbidden for symmetric excitation at the feedgap, while concomitantly the mode energy splitting is large enough to suppress excitation of the “bonding” mode. The controlled excitation of modes in strongly coupled plasmonic nanostructures is mandatory for efficient sensors, in coherent control as well as for implementing well-defined functionalities in complex plasmonic devices.

Numerical simulations and an analytic approach based on transmission line theory are used to design splitters for nano-plasmonic signal processing that allow to arbitrarily adjust the ratio of transmission from an input into two different output arms. By adjusting the geometrical parameters of the structure, either a high bandwidth or a sharp transmission resonance is obtained. Switching between the two arms can be achieved by modulating the effective refractive index of the waveguide. Employing the instantaneous Kerr effect, switching rates in the THz regime are potentially feasible. The suggested devices are of interest for future applications in nanoplasmonic information processing.

The optical phase in the feed gap of a plasmonic dipole antenna shows a transition from in-phase to counter-phase response, when its length is varied across the resonance length. We exploit this behavior in an asymmetric cross antenna structure, constituted of two perpendicular dipole antennas with different lengths, sharing the same feed gap, in order to shape the local polarization state. As an application of this concept, we propose a λ/4 nanowaveplate, able to shape and confine linearly polarized propagating waves into circularly polarized fields localized in the feed gap.

Two-photon photoluminescence (TPPL) from gold nanostructures is becoming one of the most relevant tools for plasmon-assisted biological imaging and photothermal therapy as well as for the investigation of plasmonic devices. Here we study the yield of TPPL as a function of the temporal width δ of the excitation laser pulses for a fixed average power. In the δ>1 ps regime, the TPPL yield decreases as δ is increased, while for shorter pulse widths it becomes independent of δ and, consequently, of the laser-pulse peak power. This peculiar dynamics is understood and modeled by considering that two-photon absorption in Au is a two-step process governed by the lifetime of the metastable state populated by the first photon absorption.

We propose a novel cross resonant optical antenna consisting of two perpendicular nanosized gold dipole antennas with a common feed gap. We demonstrate that the cross antenna is able to convert propagating fields of any polarization state into correspondingly polarized, localized, and enhanced fields and vice versa. The cross antenna structure therefore opens the road towards the control of light-matter interactions based on polarized light as well as the analysis of polarized fields on the nanometer scale.

We show that laser pulse shaping techniques can be applied to tailor the ultrafast temporal response of localized and propagating optical near fields in resonant optical antennas (ROAs) and plasmonic transmission lines, respectively. Using finite-difference time-domain simulations followed by Fourier transformation, we obtain the impulse response of a nanostructure in the frequency domain, which allows obtaining its temporal response to any arbitrary pulse shape. To illustrate the potential of the method we demonstrate deterministic optimal temporal pulse compression in ROAs with reduced symmetry, in a plasmonic two-wire transmission line, and in a prototype plasmonic circuit combining propagation effects and local resonances. The method described here will be of importance for the coherent control of field propagation in nanophotonic structures and light-induced processes in nanoscopic volumes.

An experimentally realizable prototype optical nanocircuit consisting of a receiving and an emitting nanoantenna connected by a two-wire optical transmission line is studied using finite-difference time- and frequency-domain simulations. To optimize the coupling between optical nanocircuit elements we apply impedance matching concepts in analogy to radio frequency technology. We show that the degree of impedance matching, and in particular the impedance of the emitting nanoantenna, can be inferred from the experimentally accessible standing wave pattern on the transmission line. We demonstrate the possibility of matching the nanoantenna impedance to the transmission line by variations of the antenna length and width realizable by modern microfabrication techniques. The radiation efficiency of the emitting antenna also depends on its geometry but is independent of the degree of impedance matching. The case study presented here provides the basis for experimental realizations of general optical nanocircuits based on readily available gold nanostructures and a large variety of derived novel devices.

We describe a method to detect and count transient burstlike signals in the presence of a significant stationary noise. To discriminate a transient signal from the background noise, an optimum threshold is determined using an iterative algorithm that yields the probability distribution of the background noise. Knowledge of the probability distribution of the noise then allows the determination of the number of transient events with a quantifiable error (wrong-positives). We apply the method, which does not rely on the choice of free parameters, to the detection and counting of transient single-molecule fluorescence events in the presence of a strong background noise. The method will be of importance in various ultra sensing applications.

We describe a simple and reliable procedure for obtaining a flat plateau on top of standard silicon nitride atomic force microscopy tips by scanning them over the focus of a high-numerical-aperture objective illuminated by near-infrared ultrashort laser pulses. Flattened tips produced this way exhibit a plateau that is parallel to the substrate when the cantilever is mounted. They represent a valid and cost-effective alternative to commercially available plateau tips.

A method for the fabrication of bow-tie optical antennas at the apex of pyramidal Si3N4 atomic force microscopy tips is described. We demonstrate that these novel optical probes are capable of sub-wavelength imaging of single quantum dots at room temperature. The enhanced and confined optical near-field at the antenna feed gap leads to locally enhanced photoluminescence (PL) of single quantum dots. Photoluminescence quenching due to the proximity of metal is found to be insignificant. The method holds promise for single quantum emitter imaging and spectroscopy at spatial resolution limited by the engineered antenna gap width exclusively.

Suitably shaped metal nano structures act as resonant optical antennas that efficiently collect light and confine it to a subwavelength volume. Vice versa, light emission from nano volumes can be enhanced by coupling to antenna structures. We give a short introduction to antenna theory and discuss recent experiments that show the feasibility of achieving strong field enhancement using resonant dipole antennas for near infrared wavelengths. By scanning an optical antenna fabricated at the apex of an AFM tip over individual quantum dots, we observe enhanced emission of the latter while it is in close proximity of the antenna feed gap. Resonant optical antennas hold promise to be applied for spectroscopic characterization of nano structures with high spatial resolutions and single-molecule sensitivity.

Simultaneous detection of single molecules by absorption and fluorescence is demonstrated using confocal microscopy at cryogenic temperature. Dynamical processes such as blinking and spectral jumping of single emitters are observed in both detection channels. The relative magnitude of fluorescence and absorption varies between molecules. In particular, we observe molecules that do not emit detectable Stokes-shifted fluorescence but show a strong absorption signal. The fact that coherent resonant scattering underlies the absorption process is demonstrated by a correlation between small linewidth and large absorption amplitude.

We investigate the dependence of the spot size in single-emitter confocal imaging on the degree of saturation. We show that single-emitter spots are broadened and flattened significantly already at excitation intensities well below saturation. The resulting single-emitter spot shapes thus deviate significantly from the excitation point spread function. We show and support by Monte Carlo simulations that fitting of a single spot is sufficient to extract the saturation intensity and the maximum emission rate of a single emitter with high accuracy. Our results will be of interest in all areas of single-emitter studies.

We investigate the interaction of hepatitis B virus capsids lacking a nuclear localization signal with nuclear pore complexes (NPCs) in permeabilized HeLa cells. Confocal and wide-field optical images of the nuclear envelope show well-spaced individual NPCs. Specific interactions of capsids with single NPCs are characterized by extended residence times of capsids in the focal volume which are characterized by fluorescence correlation spectroscopy. In addition, single-capsid-tracking experiments using fast wide-field fluorescence microscopy at 50 frames/s allow us to directly observe specific binding via a dual-color colocalization of capsids and NPCs. We find that binding occurs with high probability on the nuclear-pore ring moiety, at 44 ± 9 nm radial distance from the central axis.

Resorcin[4]arene cavitands with four quinoxaline bridges are a family of macrocycles that adopt, at elevated temperature, a contracted, vase-type conformation, capable of guest inclusion, whereas at low temperature they switch to an expanded, kite-type conformation with a large flat surface. The present investigations lay the foundation for the use of such dynamic cavitands as miniaturized mechanical grippers for supramolecular construction at the single-molecule level. New vase–kite switching modes, stimulated by pH changes or stoichiometric metal-ion complexation, have been discovered and monitored by 1H NMR and optical absorption spectroscopy. The solid-state geometries of the two states have been revealed by X-ray crystallography, and the kinetics and thermodynamics of the switching processes in solution as well as their solvent dependency has been investigated in great detail. Monolayers of the cavitand in the vase form have been studied by scanning tunneling microscopy at molecular resolution; conformational switching is also observed in Langmuir monolayers at the air/water interface. Synthetic protocols have been developed for preparation of partially and asymmetrically bridged resorcin[4]arene cavitands, which are also shown to undergo conformational switching. These synthetic advances pave the way to new, dynamic molecular receptors for steroids, tetrathiofulvalene-bridged grippers with the potential to undergo electrochemically induced conformational switching, and systems with greatly extended, rigid cavity walls functionalized at the termini by dipyrrometheneboron difluoride dyes. The latter cavitands are shown by fluorescence resonance energy transfer to undergo geometrically precisely defined motions between a contracted (≈ 7 Å linear extension) and a strongly expanded (≈ 7 nm linear extension) state.

We study the interaction of a biased, metallized tip in close proximity to single fluorescent molecules at cryogenic temperature. By scanning over the sample, the tip’s inhomogeneous electric field induces Stark shifts of the zero-phonon lines of nearby molecules. When illuminated with an off-resonant laser, molecules are tuned into resonance for specific tip positions located on circular patterns around the molecules’ spatial positions. The origins of circles belonging to different molecules can be determined with high precision. We demonstrate a spatial resolution of neighboring individual molecules of ∼50nm using a tip scanned in a distance of ∼3μm above the sample.

Single-molecule imaging and spectroscopy using an aperture scanning near-field optical microscope operating at 1.8 K in a helium bath cryostat is demonstrated. From near-field images at constant excitation frequency, the orientation of single molecules can be deduced. Spectral information is obtained using both near-field and confocal excitation schemes by scanning the excitation frequency at a fixed sample position. Differences between near-field and confocal spectra are discussed in terms of the position with respect to the aperture and the molecular orientation.

Single terrylene molecules doped into linear low-density polyethylene can be oriented by tensile deformation of the matrix. In measurements on ensembles at ambient and on single terrylene molecules at cryogenic temperature, strong orientation along the stretching direction was observed by polarization-resolved confocal microscopy. At cryogenic temperatures narrow and spectrally stable zero-phonon lines were found. The low saturation intensity of 0.07 W cm−2 is consistent with an uniaxial orientation of terrylene in the sample plane.

A scanning near-field optical microscope without any glued parts is described. Key elements are the optical fiber probe/tuning fork junction and the piezotube scanner assembly. In both cases, fixation is achieved by means of controlled pressure and elastic deformation. The avoidance of glued connections was found to improve the Q factor of the shear-force sensor as well as to facilitate the replacement of the fiber probe and other parts of the scanner head. We present approach curves and shear-force images that demonstrate the performance and stability of the system.

We theoretically study the transfer of energy from a fiber mode to surface plasmon polaritons at the silver/air interface in the taper region of a silver-coated fiber tip. We describe conditions, under which a transfer efficiency from the fiber mode to the surface plasmon polariton of up to 46% can be achieved. Propagation of the surface plasmon polaritons towards the tip of the tapered structure leads to a strong subwavelength localization of the excitation enabled by a substantial increase of the surface plasmon polariton wave vector approaching the tip. The resulting strong field enhancement and confinement has a tremendous potential for applications in ultrahigh resolution tip-enhanced near-field optical microscopy.

We report on an in vivo single-molecule study of the signaling kinetics of G protein-coupled receptors (GPCR) performed using the neurokinin 1 receptor (NK1R) as a representative member. The NK1R signaling cascade is triggered by the specific binding of a fluorescently labeled agonist, substance P (SP). The diffusion of single receptor–ligand complexes in plasma membrane of living HEK 293 cells is imaged using fast single-molecule wide-field fluorescence microscopy at 100 ms time resolution. Diffusion trajectories are obtained which show intra- and intertrace heterogeneity in the diffusion mode. To investigate universal patterns in the diffusion trajectories we take the ligand-binding event as the common starting point. This synchronization allows us to observe changes in the character of the ligand–receptor-complex diffusion. Specifically, we find that the diffusion of ligand–receptor complexes is slowed down significantly and becomes more constrained as a function of time during the first 1000 ms. The decelerated and more constrained diffusion is attributed to an increasing interaction of the GPCR with cellular structures after the ligand–receptor complex is formed.

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The interaction of a single quantum dot with a bowtie antenna is demonstrated for visible light. The antenna is generated at the apex of a Si3N4 atomic force microscopy tip by focused ion beam milling. When scanned over the quantum dot, its photoluminescence is enhanced while its excited-state lifetime is decreased. Our observations demonstrate that the relaxation channels of a single quantum emitter can be controlled by coupling to an efficiently radiating metallic nanoantenna.

We have fabricated nanometer-scale gold dipole antennas designed to be resonant at optical frequencies. On resonance, strong field enhancement in the antenna feed gap leads to white-light supercontinuum generation. The antenna length at resonance is considerably shorter than one-half the wavelength of the incident light. This is in contradiction to classical antenna theory but in qualitative accordance with computer simulations that take into account the finite metallic conductivity at optical frequencies. Because optical antennas link propagating radiation and confined/enhanced optical fields, they should find applications in optical characterization, manipulation of nanostructures, and optical information processing. Split strips of gold, each with a width of about half the wavelength of light, can act as optical antennas, capturing incident light in the gold arms and focusing the energy into the small gap. Split strips of gold, each with a width of about half the wavelength of light, can act as optical antennas, capturing incident light in the gold arms and focusing the energy into the small gap.

This paper reviews the recent progress in using single quantum systems, here mainly single fluorescent molecules, as local probes for nano–optical field distributions. We start by discussing the role of the absorption cross–section for the spatial resolution attainable in such experiments and its behaviour for different environmental conditions. It is shown that the spatial distribution of field components in a high–numerical aperture laser focus can be mapped with high precision using single fluorescent molecules embedded in a thin polymer film on glass. With this proof–of–principle experiment as a starting point, the possibility of mapping strongly confined and enhanced nano–optical fields close to material structures, e.g. sharp metal tips, is discussed. The mapping of the spatial distribution of the enhanced field at an etched gold tip using a single molecule is presented as an example. Energy transfer effects and quenching are identified as possible artefacts in this context. Finally, it is demonstrated that the local quenching at a sharp metal structure nevertheless can be exploited as a novel contrast mechanism for ultrahigh–resolution optical microscopy with single–molecule sensitivity.

We demonstrate, that under nitrogen atmosphere, 20% of single DiIC18(3) (1,1′-dioctadecyl-3,3,3′,3′-tetramethylindocarbocyanine perchlorate) molecules in poly(methylmethacrylate) show an extremely low photobleaching quantum yield of (4.66±0.07)×10−8 together with a reasonably short triplet lifetime. We exploit these properties to demonstrate that the system can be used to produce a triggered single-photon source based exclusively on organic materials.

We report the synthesis of modified Cram-type cavitands bearing one or two fluorescent labels for single-molecule spectroscopic studies of vase-kite conformational switching. Syntheses were performed by stepwise bridging of the four couples of neighboring H-bonded OH groups of resorcin[4]arene bowls. The new substitution patterns enable the construction of a large variety of future functional architectures. H-NMR Investigations showed that the new partially and differentially bridged cavitands feature temperature- and pH-triggered vase-kite conformational isomerism similar to symmetrical cavitands with four identical quinoxaline bridges. It was discovered that vase-kite switching of cavitands is strongly solvent-dependent.

We apply the concept of tomography to polarization-sensitive optical microscopy of single fluorophores to determine the three-dimensional orientation of molecular absorption dipoles with isotropic sensitivity. Wide-field microscopy provides the opportunity to monitor simultaneously three-dimensional rotation and two-dimensional translation of many molecules in parallel. For orientation determination the molecules are illuminated from different directions of incidence with linearly polarized light. In each exposure the excitation along a particular projection of the absorption dipole on the electric field leads to a distinct fluorescence intensity. Five exposures are sufficient to determine the full orientation of the fluorophores. To demonstrate the potential of the method we determine the orientation and position of individual immobilized lipid membrane markers. The shot-noise-limited isotropic angular resolution is 2°. For time-resolved studies the bandwidth can be expanded up to 200 Hz.

The fluorescence lifetime and the fluorescence rate of single molecules are recorded as a function of the position of a Si3N4 atomic force microscopy tip with respect to the molecule. We observe a decrease of the excited state lifetime and the fluorescence rate when the tip apex is in close proximity to the molecule. These effects are attributed to the fact that the dielectric tip converts non-propagating near-fields to propagating fields within the dielectric tip effectively quenching the fluorescence. The spatial extension of the quenching area is of subwavelength dimensions. The results are discussed in terms of molecular fluorescence in a system of stratified media. The experiment provides surprising new insights into the interactions between a fluorescent molecule and a dielectric tip. The methodology holds promise for applications in ultra high-resolution near-field optical imaging at the level of single fluorophores.

Microcontact printing biomolecules from elastomeric micropatterned stamps onto surfaces is a versatile method to prepare surfaces for diagnostic applications. We show how to create patterns of proteins having a lengthscale lower than 100 nm using high-resolution microcontact printing. The elastomeric stamps used have meshes composed of 100- and 40-nm-wide lines, arrays of 100 × 400 nm2 features, and arrays of 100-nm-wide posts. The spherical geometry of the posts on the stamps contributes to reduce the printed areas below the effective size of the molded features. Proteins adsorb onto the hydrophobic surface of the stamp during the inking step, and by varying the concentration of the protein solutions, it is possible to adsorb a single or a few protein molecules, such as antibodies (fluorescently labeled) or green fluorescence proteins, on each of the elements forming the high-resolution pattern of the stamp. The transfer of the proteins from the stamp to a hydrophilic glass surface occurs during the printing step. Characterization of the printed patterns using atomic force microscopy and fluorescence confocal microscopy reveals sites unoccupied or occupied by one or more protein molecules that are located within 50 nm of the expected printed locations. The placement of a small number of protein molecules on a surface at precise locations is the key to localizing and identifying single proteins and might constitute a method of choice to study single protein molecules on surfaces.

The fluorescence lifetime of single DiI-dye molecules in a 20 nm polymer film on glass is measured as a function of the orientation of the absorption dipole moment. A strong dependence of the lifetime on the orientation of the dye molecules relative to the polymer/air interface is found. Molecules with a dipole moment perpendicular to the interface exhibit a lifetime which is by a factor of 2.1±0.1 longer than the lifetime of molecules with parallel dipole moments. The general trend of the results is in good agreement with theoretical predictions. However there are significant deviations which are attributed to varying molecular environments.

The nano-optical interaction between a sharp tip and a single dipolar emitter is investigated. Changes of the excited state lifetime and the fluorescence rate of single molecules are recorded simultaneously as a function of the tip position relative to the molecule. A subdiffraction-limited area of decreased fluorescence and shortened lifetime is observed for gold-coated Si3N4 tips. The results are discussed in terms of molecular fluorescence in a system of stratified media. The outlined methodology holds promise for applications in ultrahigh-resolution near-field optical imaging at the level of single fluorophores.

We present a scanning near-field optical microscope designed for nanoscale optical imaging and spectroscopy as well as simultaneous tuning fork shear-force topographic imaging at cryogenic temperatures. The whole setup is immersed in superfluid helium (T=1.8 K). In this medium we observe resonance frequency fluctuations of the tuning fork sensor with an amplitude of Δν≈5%–10% of the full width at half-maximum of the resonance. Possible reasons for the occurrence of the frequency fluctuations are discussed. A stable gapwidth feedback can still be achieved if the set value of the frequency shift is chosen slightly larger than the fluctuation amplitude. As an example we demonstrate shear-force topographic imaging of a silicon grating in superfluid helium.

We report on the continuous measurement of fluorescence lifetimes at low light levels. Fluorescence photons following pulsed excitation generate a pulse sequence with exponentially distributed amplitudes and interphoton times at the output of a time-to-amplitude converter. This sequence is turned into a continuous step function and is time averaged with an adjustable bandwidth. For a single-exponential decay, our approach yields identical results as would be obtained from fitting fluorescence decays, while being a real-time technique. The proposed technique performs especially well at low count rates. We demonstrate the applicability of the method at the example of confocal fluorescence lifetime imaging of single molecules.

The optical near-field in the vicinity of a metal tip is mapped using a single-molecule optical probe. We observe an enhancement of the fluorescence signal by a factor of 5.7±0.3, clearly larger than the fourfold enhancement that can arise from constructive interference if the tip acts as a simple mirror. Considering the tip apex as a nanoparticle of nonregular shape, we suggest that, in the case of gold tips, the enhancement is due to resonant plasmon excitation. Consistently, no enhancement has been observed using Pt/Ir tips.

The fluorescence of single terrylene molecules in a crystalline host is investigated at room temperature by scanning confocal optical microscopy. Photon arrival times are analyzed in terms of inter-photon time distribution, second-order correlation function, and Mandel's Q-function. Nonclassical photon statistics is observed and a reverse intersystem crossing is detected that accelerates linearly with the applied laser power. Rate equations for the time evolution of the molecular level populations are shown to be appropriate for the analysis of the observations.

Single dye molecules are used as local probes to map the spatial distribution of the squared electric field components in the focus of a high numerical aperture lens. Simulated field distributions are quantitatively verified by experimentally obtained fluorescence excitation maps. We show that annular illumination can be used to engineer the field distribution in the focus at a dielectric/air interface such that electric field components in all directions acquire comparable magnitudes. The 3D orientation of molecular absorption dipoles can be determined by comparing measured to simulated image patterns. The presence of longitudinal electric field components in a focus is of particular interest in tip-enhanced scanning near-field optical microscopy.

We have applied quantitative single-molecule photoluminescence microscopy for directly observing molecular rearrangements in a polymeric material subjected to tensile deformation. The system examined is a blend of fluorescent conjugated polymer molecules embedded in polyethylene, known to exhibit strong phase separation. Statistical analysis of the sizes of phase-separated domains reveals that during tensile deformation large domains of fluorescent molecules are transformed into smaller clusters and ultimately isolated single molecules. In addition to elucidating the nature of the stretch-induced morphology change, our work underscores the fundamental value of single-molecule techniques for material analysis.

Manipulation of spectral dynamics of single molecules (SM) by a metallized scanning probe tip is demonstrated. The Stark effect of the zero-phonon lines of single pentacene molecules in a p-terphenyl host at 1.8 K is investigated by applying a voltage to the tip in contact with the sample. The measured Stark shifts exhibit a plateau and the line widths depend on the electric field. These anomalies are explained by a model based on two-level systems with field-dependent double-well potentials. The experimental data show that the two-level systems are induced by the tip.

In chemical assays, specific molecular recognition events result in close physical proximity of two molecular species, e.g., ligands and receptors. Microscopy techniques that are able to image individual molecules allow for achieving a positional accuracy far beyond the resolution limit. Therefore, independent position determination, e.g., by dual-color microscopy, becomes possible, permitting determination of intermolecular distances beyond the resolution limit. Nonzero measured distances occur due to experimental inaccuracies in case of a recognition event or due to accidental close proximity between ligand−receptor pairs. Using general statistical considerations, finite measured distances between single ligand−receptor pairs are directly translated into probabilities for true molecular recognition or mere accidental proximity. This enables a quantitative statistical analysis of single recognition events. It is demonstrated that in a general assay, even in the presence of strong unspecific background, the probability for a certain diagnosis and a measure for its reliability can be extracted from the observation of a few binding events. The power of the method is demonstrated at the example of a single-molecule DNA hybridization assay. Our findings are of major importance for future assay miniaturization and assaying with minute amounts of analyte.

The phase behavior and anisotropic optical properties of tensile deformed blends of a photoluminescent polymer guest in an ultra-high molecular weight polyethylene matrix were studied on the level of single molecules by means of scanning confocal optical microscopy. It is shown that upon tensile deformation of the blends, the system transforms from a phase-separated system into a quasi-molecular solid solution. The influence of this phase transition on the anisotropic optical properties of oriented blend films was also investigated with polarized steady-state photoluminescence spectroscopy. We show that well-dissolved guest molecules tend to reach higher degrees of orientation at lower draw ratios of the blend films compared to guests that phase-separate from the matrix polymer. Dichroic ratios in emission in the range of 50 were observed in optimized blend films based on photoluminescent oligomers and linear low density polyethylene.

The absorption dipole orientation of single fluorescent molecules is determined by mapping the spatial distribution of the squared electric field components in a high-numerical-aperture laser focus. Annular illumination geometry and the vicinity of a plane dielectric/air interface strongly enhance the longitudinal field component and the transverse fields perpendicular to the polarization direction. As a result, all three excitation field components in the focus are of comparable magnitude. The scheme holds promise to monitor rotational diffusion of single molecules in complex environments.

We have investigated the luminescence of CaF2 thin films doped with very low concentrations of Sm2+ ions using scanning confocal optical microscopy at low temperatures. The film morphology was studied independently by atomic force microscopy. The Sm2+ ions are homogeneously distributed in the films and show photobleaching. Unexpectedly, on the film surface strongly luminescent small topographic features are observed that are found to contain Sm3+ by spectral analysis. The formation of Sm3+ is probably due to the presence of oxygen during film growth. In the lowest doped films on-off blinking behavior of isolated luminescent spots provides strong evidence for the first observation of single ions in a crystal.

Photoluminescence microscopy of conjugated polymer molecules in a polyethylene host has been applied to monitor the transition of a phase-separated polymer blend into a molecular dispersion induced by solid-state tensile deformation. Statistical analysis of conjugated polymer cluster sizes as a function of the degree of matrix deformation shows that phase-separated domains of conjugated polymer transform into smaller clusters and single molecules as the degree of matrix deformation increases. Concomitantly, the conjugated guest molecules tend to adopt the preferential orientation of the surrounding matrix. We demonstrate that single-molecule detection can be readily extended and applied to probing molecular dispersion, orientation, and morphology in polymer−polymer blends.

In this review we describe fundamentals of scanning near-field optical microscopy with aperture probes. After the discussion of instrumentation and probe fabrication, aspects of light propagation in metal-coated, tapered optical fibers are considered. This includes transmission properties and field distributions in the vicinity of subwavelength apertures. Furthermore, the near-field optical image formation mechanism is analyzed with special emphasis on potential sources of artifacts. To underline the prospects of the technique, selected applications including amplitude and phase contrast imaging, fluorescence imaging, and Raman spectroscopy, as well as near-field optical desorption, are presented. These examples demonstrate that scanning near-field optical microscopy is no longer an exotic method but has matured into a valuable tool.

A sample-scanning confocal optical microscope for single-molecule imaging and spectroscopy working at superfluid helium temperature, liquid nitrogen, and room temperature is described. An optical resolution of 800 nm full width at half maximum as well as a detection efficiency of ≈3.5% are achieved. The sample scanner features an exceptionally large scan range of 23 μm at 1.8 K. A position sensor allows for continuous observation of the scanner motion and for a correction of piezoelectric hysteresis and creep at 77 K and at room temperature. Coarse positioning of the sample in x-y is achieved by an inertia drive with high reproducibility and nanometer precision. We demonstrate combined high–resolution confocal imaging and spectroscopy of single molecules at 1.8 K.

A method to identify single molecules rapidly and with high efficiency based on simple probability considerations is proposed. In principle, any property of a detected photon in a single-molecule fluorescence experiment, e.g., emission wavelength, arrival time after pulsed excitation, and polarization, can be analyzed within the framework of the outlined methodology. Monte Carlo simulations show that less than 500 photons are needed to assign an observed single molecule to one out of four species with a confidence level higher than 99.9%. We show that single dye molecules of four different dyes embedded in a polymer film can be identified with time-correlated single-photon counting spectrally resolved in two channels.

The fluorescence of single terrylene molecules in a crystalline host is investigated at room temperature by scanning confocal optical microscopy. Photon arrival times are analyzed in terms of interphoton time distributions, second order correlation functions, and the variance of the photon number probability distribution. Antibunching at short times and bunching behavior for longer times is observed, associated with sub- and super-Poissonian statistics, respectively. A rate-equation analysis of the molecular level populations indicates an accelerated reverse intersystem crossing.

A method called tube etching for the fabrication of near-field optical probes is presented. Tip formation occurs inside a cylindrical cavity formed by the polymer coating of an optical fiber which is not stripped away prior to etching in hydrofluoric acid. The influence of temperature, etchant concentration, and fiber type on the tip quality is studied. A tip formation mechanism for the given geometry is proposed. The procedure overcomes drawbacks of the conventional etching techniques while still producing large cone angles: (i) tips with reproducible shapes are formed in a high yield, (ii) the surface roughness on the taper is drastically reduced, and (iii) the tip quality is insensitive to vibrations and temperature fluctuations during the etching process. After aluminum coating, optical probes with well-defined apertures are obtained. Due to the smooth glass surface the aluminum coating is virtually free of pinholes.

Scanning near-field optical microscopy (SNOM) has pushed today’s optical resolution limit to about 20 nm, with a potential for improvement by another order of magnitude still remaining. SNOM provides chemical specificity based on spectral (amplitude, phase), polarization, and/or fluorescence contrast; it also allows dynamic studies with femtosecond time resolution and photochemistry on the nanometer scale. In spite of these prospects and considerable ongoing research efforts, progress in near-field optical microscopy has been rather slow in the past few years.