Nanoscale resolved infrared probing of crystal structure and of plasmon-phonon coupling

We show that slight variations of a crystal lattice cause significant spectral modifications of phonon-polariton resonant near-field interaction between polar semiconductor crystals and a scanning metal tip. Exploiting the effect for near-field imaging a SiC polytype boundary, we establish infrared mapping of crystal structure and crystal defects at 20 nm spatial resolution (lambda/500). By spectroscopic probing of doped SiC polytypes, we find that phonon-polariton resonant near-field interaction is also sensitive to electronic properties due to plasmon-phonon coupling in the crystals.     

Near-field microscopy by elastic light scattering from a tip

We describe ultraresolution microscopy far beyond the classical Abbe diffraction limit of one half wavelength (lambda/2), and also beyond the practical limit (ca. lambda/10) of aperture-based scanning near-field optical microscopy (SNOM). The 'apertureless' SNOM discussed here uses light scattering from a sharp tip (hence scattering-type or s-SNOM) and has no lambda-related resolution limit. Rather, its resolution is approximately equal to the radius a of the probing tip (for commercial tips, a < 20 nm) so that 10 nm is obtained in the visible (lambda/60). A resolution of lambda/500 has been obtained in the mid-infrared at lambda = 10 microm. The advantage of infrared, terahertz and even microwave illumination is that specific excitations can be exploited to yield specific contrast, e.g. the molecular vibration offering a spectroscopic fingerprint to identify chemical composition. S-SNOM can routinely acquire simultaneous amplitude and phase images to obtain information on refractive and absorptive properties. Plasmon- or phonon-resonant materials can be highlighted by their particularly high near-field signal level. Furthermore, s-SNOM can map the characteristic optical eigenfields of small, optically resonant particles. Lastly, we describe theoretical modelling that explains and predicts s-SNOM contrast on the basis of the local dielectric function.     

Material-specific infrared recognition of single sub-10 nm particles by substrate-enhanced scattering-type near-field microscopy

We study the optical material contrast of single nanoparticles in infrared scattering-type near-field optical microscopy (IR s-SNOM) in the presence of strong probe-substrate coupling. It is shown theoretically and experimentally that the contrast depends on both the dielectric properties of the nanoparticles and on their size. We can separate the two dependencies by correlating the simultaneously acquired topography and near-field images pixel-by-pixel. This allows us to establish material-specific mapping of polydisperse nanoparticle mixtures with nanoscale spatial resolution. We experimentally demonstrate the differentiation between sub-10 nm gold and polymer particles adsorbed on a Si substrate. Possible applications of our method range from the material-specific mapping of nanoparticle assemblies to the measurement of the doping concentration in single semiconductor nanoparticles.     

Towards terahertz near-field microscopy

We have detected sub-wavelength spot sizes in the near-field of a metal tip, which is illuminated with terahertz (THz) pulses. The THz near-field is detected by using electro-optic detection in a (100) oriented GaP crystal. Contrary to conventional electro-optic detection, which uses (110) oriented detection crystals, (100) crystals only allow the detection of THz light, polarized perpendicular to our crystal surface. This component is strongly localized near the apex of the tip, which has sub-wavelength dimensions. The detection process is blind to the incident THz radiation, which is polarized parallel to the crystal surface. As a result, a sub-wavelength THz spot size with an intensity full-width half maximum (FWHM) diameter of lambda/200 is observed.     

Near-field thermal lens detection at 257 nm as an alternative to absorption spectrometric detection in combination with electromigrative separation techniques

A device is presented that permits detection of analytes absorbing electromagnetic radiation at lambda = 257 nm (in fused-silica capillaries with 75-microm i.d.) via the near-field thermal lens effect. The detector was realized by using a frequency-doubled argon ion laser as pump laser and a laser diode (emission wavelength, 633 nm) coupled into a monomode optical fiber as probe laser. Comparing the performance of this detector to the performance of a commercial absorption spectrometric detector working at lambda = 257 nm equipped with a unit for on-column detection in fused-silica capillaries showed a substantial improvement in detection limits (up to 30-fold improvement) for the near-field thermal lens detector (NF-TLD). The feasibility of the NF-TLD for sensitive detection of nonfluorescent analytes in real samples after separation by micellar electrokinetic chromatography was shown taking the determination of nitroaromatic compounds in contaminated water from a former ammunition plant as an example. Dependence of the thermal lens signal on pump laser power, velocity of the mobile phase, and chopper frequency was investigated. A linear calibration range over 2 orders of magnitude was obtained.     

Two particle enhanced nano Raman microscopy and spectroscopy

The distance- and polarization-dependent near-field enhancement of two coupling metal nanoparticles (MNPs) is analyzed by means of the novel scanning particle enhanced Raman spectroscopy (SPRM) technique. In contrast to single MNP Raman experiments, the near-field coupling between two dissimilar MNPs as followed here leads to a Raman hot spot yielding an extra enhancement factor of 17.6 and 20, as proven here both in experiment and in theory. Three-dimensional electric field calculations for our two-particle arrangements were performed using the semianalytical multiple-multipole method. An excellent agreement is found to our experiments, in which we inspect the interaction between a "scanning" 30 nm gold MNP (Au30) and a "fixed" 80 nm Au MNP (Au80). The Au80 MNP is attached to the apex of an optical fiber manipulator and exposed to the Gaussian focus of a high NA = 1.45 objective at lambda = 532 nm. A monolayer of 1-octanethiol molecules covering the Au80 MNP serves as the electric field prober when scanning the Au30 MNP through the optical focus. This constellation allows recording the Raman signatures from a very low number of well-confined molecules. Moreover, also the spectral and spatial dependence could be explored with a superb sensitivity and very low integration time.     

Nanometer-scale dielectric imaging of semiconductor nanoparticles: size-dependent dipolar coupling and contrast reversal

Scattering-type apertureless near-field microscopy (ANSOM) provides high-resolution dielectric maps of indium gallium nitride (InGaN) semiconductor nanoparticles at visible (633 nm) wavelengths. A specific size-dependent contrast reversal is observed in the ANSOM images of InGaN nanoparticles grown on a layer of gallium nitride (GaN). Model calculations demonstrate that the observed contrast reversal is the result of the competition between the tip-particle versus tip-substrate dipolar coupling.     

Quantification of etoposide and etoposide phosphate in human plasma by micellar electrokinetic chromatography and near-field thermal lens detection

A method employing micellar electrokinetic chromatography in combination with near-field thermal lens detection (NF-TLD) was developed for the rapid simultaneous determination of etoposide phosphate and etoposide in human blood plasma, taking teniposide as internal standard. The method developed allows the baseline separation of the solutes of interest from each other and from potential interfering matrix constituents within 4 min. The NF-TLD device employed permits detection of solutes absorbing electromagnetic radiation at lambda = 257 nm in fused-silica capillaries with 75-microm i.d. via the near-field thermal lens effect with LODs of 100 microg L(-1) for etoposide phosphate and 170 microg L(-1) for etoposide. Comparison of the performance of this detector to the performance of a commercial absorption spectrometric detector working at lambda = 257 nm showed a substantial improvement in detection limits (up to 60-fold improvement) for the near-field thermal lens detector.     

Adiabatic nanofocusing scattering-type optical nanoscopy of individual gold nanoparticles

We explore imaging of local electromagnetic fields in the vicinity of metallic nanoparticles using a grating-coupled scattering-type near-field scanning optical microscope. In this microscope, propagating surface plasmon polariton wavepackets are launched onto smooth gold tapers where they are adiabatically focused toward the nanometer-sized taper apex. We report two-dimensional raster-scanned optical images showing pronounced near-field contrast and demonstrating sub-30 nm resolution imaging of localized surface plasmon polariton fields of spherical and elliptical nanoparticles. By comparison to three-dimensional finite-difference time domain simulations, we conclude that virtually background-free near-field imaging is achieved. The microscope combines deep subwavelength resolution, high local field intensities and a straightforward imaging contrast, making it interesting for a variety of applications in linear and nonlinear nanospectroscopy.     

Near-field microscopy and lithography of light-emitting polymers

We describe the application of scanning near-field optical microscopy (SNOM) to the study of the photophysical and self-organization properties of thin films of blends of conjugated polymers, and also to the lateral nanoscale patterning of conjugated-polymer structures. Such thin-film plastic semiconductor nanostructures offer significant potential for use in opto-electronic devices. The implementation of SNOM we employ is the most established form in which a probe with a sub-wavelength aperture is scanned in close proximity to the sample surface. We consider the nature of the near-field optical distribution, which decays within the first ca. 100 nm of these semiconductor materials, and address the identification of topographic artefacts in near-field optical images. While the topographic information obtained simultaneously with optical data in any SNOM experiment enables an easy comparison with the higher-resolution tapping-mode atomic force microscopy, the spectroscopic contrast provided by fluorescence SNOM gives an unambiguous chemical identification of the different phases in a conjugated-polymer blend. Both fluorescence and photoconductivity SNOM indicate that intermixing of constituent polymers in a blend, or nanoscale phase separation, is responsible for the high efficiency of devices employing these materials as their active layer. We also demonstrate a scheme for nano-optical lithography with SNOM of conjugated-polymer structures, which has been employed successfully for the fabrication of poly(-phenylene vinylene) nanostructures with 160 nm feature sizes.     

Analysing one isolated single walled carbon nanotube in the near-field domain with selective nanovolume Raman spectroscopy

In this paper, we describe a new method to the selective nanovolume analysing of one isolated single walled carbon nanotube (SWNT). This concept is based on actually available imaging micro-spectrometry systems for working in near-field domain combined with a stigmatic solid immersion lens. This combination of different analytical methods, and modified and configured equipment entitles us to expand the functionality toward a three-dimensional (3D) nanovolume Raman mapping and photoluminescence intensity with a possible discrimination in polarization, as well as photoluminescence decaytime constant mapping with their unique combination. Subsequently, selective spectra can be acquired from the same location on the samples. By spectrally selecting a SWNT, we registered the spatial distribution of the emitted photons in x, y, z vectors to determine the position of a SWNT in the near-field domain. For the SWNTs that are localized with an accuracy better than 18 nm in the x, y and <1 nm in the z directions, we demonstrate an analytical sensitivity close to a single nanotube with unity throughput. This near-field capability is applied to resolve local variations unambiguously in the Raman spectrum along one single SWNT. Finally, in this paper, we report what we believe to be the first evidence of Raman mapping and 3D real optical imaging of carbon nanotubes with near-field resolution.     

Few-cycle terahertz generation and spectroscopy of nanostructures

We report on new schemes for terahertz (THz) generation. The THz efficiency of photoconducting antennas can be increased by using a cavity effect for the near-infrared pump beam. The cavity is formed by a molecular beam epitaxy grown semiconductor Bragg mirror below the photoconducting layer. The optical confinement is accompanied by an electrical confinement suppressing undesired leakage currents and providing a constant electric field in the active layers. The performance of this cavity-enhanced emitter is further improved by using a mobility optimized low-temperature GaAs layer. This emitter is successfully used in a femtosecond Ti:sapphire laser cavity for highly efficient intracavity THz generation, where the photoconductive layer serves also as a saturable absorber. The broadband THz pulses generated are used for time-resolved spectroscopy of nanostructures. We study the dynamics of intersubband transitions in semiconductor quantum wells. The relaxation of carriers excited by a near-infrared pump pulse is investigated by measuring the THz absorption between the different subbands with our THz pulses. For transition energies below the optical phonon energy we find relatively long relaxation times with a strong dependence on the excited carrier density.     

Characteristics of III-nitride photodiodes with self-assembled quantum dots

In this work, it has been demonstrated that metal–semiconductor–metal (MSM) photodiodes (PDs) with InGaN self-assembled quantum dots (QDs) were fabricated and compared with conventional InGaN MSM photodiodes. The scanning near-field optical microscope (SNOM) results revealed that such InGaN nanostructures could have better absorption for the near-field light with the wavelength of 457–514 nm. It was found that the InGaN QD photodiode with lower dark current can operate in the normal incidence mode; we could achieve a much larger photocurrent to dark current contrast ratio from MSM photodiodes with nanoscale InGaN quantum dots. It was also found that the measured responsivity of MSM photodiodes with QDs and without QDs approximated to the same in the range of 390–460 nm. Furthermore, the photodiodes with QDs showed higher spectral response than that of the photodiodes without QDs at wavelengths < 350 nm and > 480 nm.     

Assessing charge carrier trapping in silicon nanowires using picosecond conductivity measurements

Free-standing semiconductor nanowires on bulk substrates are increasingly being explored as building blocks for novel optoelectronic devices such as tandem solar cells. Although carrier transport properties, such as mobility and trap densities, are essential for such applications, it has remained challenging to quantify these properties. Here, we report on a method that permits the direct, contact-free quantification of nanowire carrier diffusivity and trap densities in thin (～25 nm wide) silicon nanowires-without any additional processing steps such as transfer of wires onto a substrate. The approach relies on the very different terahertz (THz) conductivity response of photoinjected carriers within the silicon nanowires from those in the silicon substrate. This allows quantifying both the picosecond dynamics and the efficiency of charge carrier transport from the silicon nanowires into the silicon substrate. Varying the excitation density allows for quantification of nanowire trap densities: for sufficiently low excitation fluences the diffusion process stalls because the majority of charge carriers become trapped at nanowire surface defects. Using a model that includes these effects, we determine both the diffusion constant and the nanowire trap density. The trap density is found to be orders of magnitude larger than the charge carrier density that would be generated by AM1.5 sunlight.     

Near-field visualization of strongly confined surface plasmon polaritons in metal-insulator-metal waveguides

A nanoscale gap between two metal surfaces can confine propagating surface plasmon polaritons (SPPs) to very small dimensions, but this geometry makes it inherently difficult to image SPP propagation at high resolution. We demonstrate the near-field probing of these SPPs, propagating within a 50 nm thick Si 3N 4 waveguide with Ag cladding layers for frequencies ranging from the blue to the near-infrared. Using near-field SPP interferometry, we determine the wave vector, showing that the wavelength is shortened to values as small as 156 nm for a free-space wavelength of 532 nm.     

Terahertz pulse propagation in the near field and the far field

We present a detailed investigation of the propagation properties of beams of ultrashort terahertz (THz) pulses emitted from large-aperture (LA) antennas. The large area of the emitter is demonstrated to have substantial influence on the temporal pulse profile in both the near field and the far field. We perform a numerical analysis based on scalar and vectorial broadband diffraction theory and are able to distinguish between near-field and far-field contributions to the total THz signal. We find that the THz beam from a LA antenna propagates like a Gaussian beam and that the temporal profile of the THz pulse, measured in the near field, contains information about the temporal and spatial field distribution on the emitter surface, which is intrinsically connected to the carrier dynamics of the antenna substrate. As a result of pulse reshaping, focusing of the THz beam leads to a reduced relative pulse momentum, with implications in THz field-ionization experiments.     

Intersublevel Spectroscopy on Single InAs-Quantum Dots by Terahertz Near-Field Microscopy

Using scattering-type near-field infrared microscopy in combination with a free-electron laser, intersublevel transitions in buried single InAs quantum dots are investigated. The experiments are performed at room temperature on doped self-assembled quantum dots capped with a 70 nm GaAs layer. Clear near-field contrast of single dots is observed when the photon energy of the incident beam matches intersublevel transition energies, namely the p-d and s-d transition of conduction band electrons confined in the dots. The observed room-temperature line width of 5-8 meV of these resonances in the mid-infrared range is significantly below the inhomogeneously broadened spectral lines of quantum dot ensembles. The experiment highlights the strength of near-field microspectroscopy by demonstrating signals from bound-to-bound transitions of single electrons in a probe volume of the order of (100 nm)(3).     

Extraordinary optical transmission brightens near-field fiber probe

Near-field scanning optical microscopy (NSOM) offers high optical resolution beyond the diffraction limit for various applications in imaging, sensing, and lithography; however, for many applications the very low brightness of NSOM aperture probes is a major constraint. Here, we report a novel NSOM aperture probe that gives a 100× higher throughput and 40× increased damage threshold than conventional near-field aperture probes. These brighter probes facilitate near-field imaging of single molecules with apertures as small as 45 nm in diameter. We achieve this improvement by nanostructuring the probe and by employing a novel variant of extraordinary optical transmission, relying solely on a single aperture and a coupled waveguide. Comprehensive electromagnetic simulations show good agreement with the measured transmission spectra. Due to their significantly increased throughput and damage threshold, these resonant configuration probes provide an important step forward for near-field applications.     

Observation of nanostructure by scanning near-field optical microscope with small sphere probe

Step and terrace structure has been observed in an area of 1 μm×1 μm on the cleaved surface of KCl-KBr solid-solution single crystal by scanning near-field optical microscope (SNOM) with a small sphere probe of 500 nm diameter. Lateral spatial resolution of the SNOM system was estimated to be 20 nm from the observation of step width and the scanning-step interval. Vertical spatial resolution was estimated to be 5-2 nm from the observation of step height and noise level of photomultiplier tube (PMT). With applying a dielectric dipole radiation model to the probe surface, the reason why such a high spatial resolution was obtained in spite of the 500 nm sphere probe, was understood as the effect of the near-field term appeared in the radiation field equations.     

Mapping the plasmon resonances of metallic nanoantennas

We study the light scattering and surface plasmon resonances of Au nanorods that are commonly used as optical nanoantennas in analogy to dipole radio antennas for chemical and biodetection field-enhanced spectroscopies and scanned-probe microscopies. With the use of the boundary element method, we calculate the nanorod near-field and far-field response to show how the nanorod shape and dimensions determine its optical response. A full mapping of the size (length and radius) dependence for Au nanorods is obtained. The dipolar plasmon resonance wavelength lambda shows a nearly linear dependence on total rod length L out to the largest lengths that we study. However, L is always substantially less than lambda/2, indicating the difference between optical nanoantennas and long-wavelength traditional lambda/2 antennas. Although it is often assumed that the plasmon wavelength scales with the nanorod aspect ratio, we find that this scaling does not apply except in the extreme limit of very small, spherical nanoparticles. The plasmon response depends critically on both the rod length and radius. Large (500 nm) differences in resonance wavelength are found for structures with different sizes but with the same aspect ratio. In addition, the plasmon resonance deduced from the near-field enhancement can be significantly red-shifted due to retardation from the resonance in far-field scattering. Large differences in near-field and far-field response, together with the breakdown of the simple scaling law must be accounted for in the choice and design of metallic lambda/2 nanoantennas. We provide a general, practical map of the resonances for use in locating the desired response for gold nanoantennas.