Diffraction-limited hyperspectral mid-infrared micro-ellipsometry.

The recent introduction of quantum cascade lasers (QCL) in infrared spectroscopic ellipsometry led to decisive improvements in measurement times and signal-to-noise ratios of this powerful analytical method. In this contribution, we present another significant enhancement leading to the first, to the best of our knowledge, diffraction-limited micro-ellisometry setup in the mid-infrared spectral range with a spatial resolution better than 13.3 µm. The fast spectral tunability of the QCL combined with phase-modulated polarization enabled simultaneous acquisition of broadband (900 cm-1-1204 cm-1) high-resolution (1 cm-1) hyperspectral Ψ, Δ-cubes in a scanning approach in reasonable time scales. The spatial resolution of the QCL micro-ellipsometer was experimentally characterized by the knife-edge method and measurements of a resolution test target. Furthermore, the hyperspectral ellipsometric investigation of a polymer multilayer cross section and the portrait window of a 200-euro bank note demonstrate the capabilities of diffraction-limited QCL micro-ellipsometry.

Layered gallium sulfide optical properties from monolayer to CVD crystalline thin films.

Interest in layered van der Waals semiconductor gallium monosulfide (GaS) is growing rapidly because of its wide band gap value between those of two-dimensional transition metal dichalcogenides and of insulating layered materials such as hexagonal boron nitride. For the design of envisaged optoelectronic, photocatalytic and photonic applications of GaS, the knowledge of its dielectric function is fundamental. Here we present a combined theoretical and experimental investigation of the dielectric function of crystalline 2H-GaS from monolayer to bulk. Spectroscopic imaging ellipsometry with micron resolution measurements are corroborated by first principle calculations of the electronic structure and dielectric function. We further demonstrate and validate the applicability of the established dielectric function to the analysis of the optical response of c-axis oriented GaS layers grown by chemical vapor deposition (CVD). These optical results can guide the design of novel, to our knowledge, optoelectronic and photonic devices based on low-dimensional GaS.

Model for the depolarizing retarder in Mueller matrix polarimetry.

We advance an analytical model describing the polarimetric response of a depolarizing retarder whose retardance varies spatially in magnitude or in orientation. The variation of the retarder parameters may be either of deterministic or of random nature. The model provides both the mean values and the uncertainties of the parameters. Its application is illustrated on two experimental examples, respectively covering the deterministic and the random cases.

Sub-second quantum cascade laser based infrared spectroscopic ellipsometry.

Laser-based infrared spectroscopic ellipsometry (SE) is demonstrated for the first time, to the best of our knowledge, by applying a tunable quantum cascade laser (QCL) as a mid-infrared light source. The fast tunability of the employed QCL, combined with phase-modulated polarization, enabled the acquisition of broadband (900-1204 cm-1), high-resolution (1 cm-1) ellipsometry spectra in less than 1 second. A comparison to a conventional Fourier-transform spectrometer-based IR ellipsometer resulted in an improved signal-to-noise ratio (SNR) by a factor of at least 290. The ellipsometry setup was finally applied for the real-time monitoring of molecular reorientation during the stretching process of an anisotropic polypropylene film, thereby illustrating the advantage of sub-second time resolution. The developed method exceeds existing instrumentation by its fast acquisition and high SNR, which could open up a set of new applications of SE such as ellipsometric inline process monitoring and quality control.

Thermally stable coexistence of liquid and solid phases in gallium nanoparticles.

Gallium (Ga), a group III metal, is of fundamental interest due to its polymorphism and unusual phase transition behaviours. New solid phases have been observed when Ga is confined at the nanoscale. Herein, we demonstrate the stable coexistence, from 180 K to 800 K, of the unexpected solid γ-phase core and a liquid shell in substrate-supported Ga nanoparticles. We show that the support plays a fundamental role in determining Ga nanoparticle phases, with the driving forces for the nucleation of the γ-phase being the Laplace pressure in the nanoparticles and the epitaxial relationship of this phase to the substrate. We exploit the change in the amplitude of the evolving surface plasmon resonance of Ga nanoparticle ensembles during synthesis to reveal in real time the solid core formation in the liquid Ga nanoparticle. Finally, we provide a general framework for understanding how nanoscale confinement, interfacial and surface energies, and crystalline relationships to the substrate enable and stabilize the coexistence of unexpected phases.

Bulk quadrupole contribution to second harmonic generation from classical oscillator model in silicon.

We predict the frequency-dependent bulk quadrupole contribution to second harmonic generation in silicon quantitatively from the linear susceptibility by means of a generalized classical anharmonic oscillator model and the simplified bond hyperpolarizability model. We show that in single-beam setups the main contribution is found for the silicon (111) surface, and only a minor contribution for the (001) and (011) facets. The dipole contribution obtained from our model is compared to literature values for SiC, AlAs and GaAs to demonstrate the viability of the method.

Experimental evidence for partial spatial coherence in imaging Mueller polarimetry.

We demonstrate experimentally the validity of the partial spatial coherence formalism in Mueller polarimetry and show that, in a finite spatial resolution experiment, the measured response is obtained through convolving the theoretical one with the instrument function. The reported results are of primary importance for Mueller imaging systems.

General approach for modeling partial coherence in spectroscopic Mueller matrix polarimetry.

We present a general formalism for modeling partial coherence in spectroscopic Mueller matrix measurements of stratified media. The approach is based on the statistical definition of a Mueller matrix, as well as, on the fundamental representation of the measurement process as the convolution of the sample response with a specific instrumental function. The formalism is readily extended to describe other measurement imperfections occurring jointly with partial coherence and resulting in depolarizing experimental Mueller matrices.

General formalism for partial spatial coherence in reflection Mueller matrix polarimetry.

Starting from the first principles, we derive the expressions governing partially coherent Mueller matrix reflection polarimetry on spatially inhomogeneous samples. These are reported both in their general form and in the practically important specific form for two juxtaposed media.

Giant cross polarization in a nanoimprinted metamaterial combining a fishnet with its Babinet complement.

We present a large area (1 cm2) nanoimprinted metamaterial comprising a fishnet structure and its Babinet complement, which shows giant cross polarization. When illuminated with s-polarized light, the reflected beam can be p-polarized up to 96%, depending on the azimuthal orientation of the sample. This experimental result is close to the result of numerical simulations, which predict 98.7% of cross-polarization. It is further shown, that 95-100% cross polarization is only achieved in the case when the fishnet is combined with its Babinet complement. Each structure alone (either an ordinary fishnet or a plane with metallic rectangles only) shows substantially less polarization conversion.

Chloride-induced morphology transformations of the Cu(110) surface in dilute HCl.

Morphological changes of a bare Cu(110) substrate in 10 mM HCl aqueous solution have been studied using cyclic voltammetry (CV), electrochemical scanning tunneling microscopy (EC-STM), and reflectance anisotropy spectroscopy (RAS). At cathodic potentials more positive than the hydrogen evolution reaction, a bare copper surface (1 × 1) structure is found by EC-STM. At anodic potentials more negative than the copper(II) dissolution reaction, a furrowed structure is found. The governing factor that rules Cu(110)-Cl interface processes is discussed as an interplay among Cl(-) adsorption/desorption, the dynamic rearrangement of the surface atoms on the substrate, and strain in order to reduce the surface energy. The information provided by EC-STM and RAS complements that of CV, supplies detailed information on the surface morphology, and correlates peaking Faraday currents to structural modifications. Furthermore, RAS and EC-STM show changes in the surface appearance in a potential range where no specific charge transfer is observed. CV indicates that the Cu(110) surface chemistry compares much better to that of amorphous Cu than to that of the more stable (100) and (111) surfaces, respectively.

Photoelectrochemical scanning droplet cell microscopy for localized photovoltaic investigations on organic semiconductors.

Photoelectrochemical characterization of the regioregular poly(3-hexylthiophene) (P3HT) was performed using an adapted version of a photoelectrochemical scanning droplet cell microscope (PE-SDCM). The real and imaginary parts of the dielectric function were determined using spectroscopic ellipsometry in order to identify the absorption region of the polymer. Detailed photoelectrochemical experiments were performed for the thin polymer layer contacted with 0.1 M tetrabutylammonium hexafluorophosphate dissolved in propylene carbonate as well as with an electrolyte containing a 5.4 mM ferrocene/ferrocenium redox couple. The effect of the illumination on the P3HT covered WE in contact with both the pure electrolyte and an electrolyte containing a ferrocene/ferrocenium redox couple was studied using dark/illumination sequences. The stability of the photovoltaic effect was characterized using long term current transients. Finally, the photoelectrochemical impedance spectroscopy was applied to determine the electrical properties of the P3HT in the dark and under illumination.

Prediction of First-Order Phase Transition with Electron-Phonon Interaction.

Phase transitions in solids occur due to the shifting balance between the binding energies and entropic contributions of different crystal structures, even though the underlying Hamiltonian remains the same. This work demonstrates that incorporating electron-phonon interactions in the Hamiltonian results in distinct free energies at different temperatures, thus leading to a first-order phase transition. Contrary to prior investigations, taking into consideration the quantum mechanical kinetic energy operator of the nucleus by employing Bogoliubov's inequality yields a first-order phase transition. An equation is implicitly derived to determine the critical temperature of the first-order phase transition. Furthermore, an estimation is made to evaluate the latent heat and the resulting positional displacement of the nucleus. Comparing the present findings with previous ones allows setting parameter boundaries for both first- and second-order phase transitions.

Surface morphology, optical properties and conductivity changes of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) by using additives.

The optical properties and electrical conductivity of highly conducting poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrenesulfonate) (PSS) are reported as a function of the processing additive conditions. The addition of dimethyl sulfoxide (DMSO) increases the conductivity and modifies the dielectric response as observed from the ellipsometric studies. Also the surface roughness and morphology change with the composition of PEDOT:PSS:DMSO and film deposition conditions. The real part of the dielectric function becomes negative in highly conducting samples, indicating the presence of delocalized charge carriers. The real and imaginary parts of the refractive index were determined as a function of wavelength. The results are consistent with the increase in conductivity upon the addition of DMSO.

Increasing the Stability of Isolated and Dense High-Aspect-Ratio Nanopillars Fabricated Using UV-Nanoimprint Lithography.

Structural anti-reflective coating and bactericidal surfaces, as well as many other effects, rely on high-aspect-ratio (HAR) micro- and nanostructures, and thus, are of great interest for a wide range of applications. To date, there is no widespread fabrication of dense or isolated HAR nanopillars based on UV nanoimprint lithography (UV-NIL). In addition, little research on fabricating isolated HAR nanopillars via UV-NIL exists. In this work, we investigated the mastering and replication of HAR nanopillars with the smallest possible diameters for dense and isolated arrangements. For this purpose, a UV-based nanoimprint lithography process was developed. Stability investigations with capillary forces were performed and compared with simulations. Finally, strategies were developed in order to increase the stability of imprinted nanopillars or to convert them into nanoelectrodes. We present UV-NIL replication of pillars with aspect ratios reaching up to 15 with tip diameters down to 35 nm for the first time. We show that the stability could be increased by a factor of 58 when coating them with a 20 nm gold layer and by a factor of 164 when adding an additional 20 nm thick layer of SiN. The coating of the imprints significantly improved the stability of the nanopillars, thus making them interesting for a wide range of applications.

Evidence of plasmonic coupling in gallium nanoparticles/graphene/SiC.

Graphene is emerging as a promising material for plasmonics applications due to its strong light-matter interactions, most of which are theoretically predicted but not yet experimentally realized. Therefore, the integration of plasmonic nanoparticles to create metal nanoparticle/graphene composites enables numerous phenomena important for a range of applications from photonics to catalysis. For these applications it is important to articulate the coupling of photon-based excitations such as the interaction between plasmons in each of the material components, as well as their charge-based interactions dependent upon the energy alignment at the metal/graphene interface. These coupled phenomena underpin an active application area in graphene-based composites due to nanoparticle-dependent surface-enhanced Raman scattering (SERS) of graphene phonon modes. This study reveals the coupling of a graphene/SiC support with Ga-nanoparticle-localized surface plasmon resonance, which is of particular interest due to its ability to be tuned across the UV into the near-IR region. This work is the first demonstration of the evolving plasmon resonance on graphene during the synthesis of surface-supported metal nanoparticles, thus providing evidence for the theoretically predicted screening revealed by a damped resonance with little energy shift. Therefore, the role of the graphene/substrate heterojunction in tailoring the plasmon resonance for nanoplasmonic applications is shown. Additionally, the coupled phenomena between the graphene-Ga plasmon properties, charge transfer, and SERS of graphene vibrational modes are explored.

Oblique incidence ellipsometric characterization and the substrate dependence of visible frequency fishnet metamaterials.

We use spectroscopic ellipsometry to investigate the angular-dependent optical modes of fishnet metamaterials fabricated by nanoimprint lithography. Spectroscopic ellipsometry is demonstrated as a fast and efficient method for metamaterial characterization and the measured polarization ratios significantly simplify the calibration procedures compared to reflectance and transmittance measurements. We show that the modes can be well identified by a combination of comparing different substrates and considering the angular dependence of the Wood's anomalies. The lack of angular dispersion of the anti-symmetric gap-modes does not agree with the model and requires further theoretical investigation.

Interlaboratory study on Sb2S3 interplay between structure, dielectric function, and amorphous-to-crystalline phase change for photonics.

Antimony sulfide, Sb2S3, is interesting as the phase-change material for applications requiring high transmission from the visible to telecom wavelengths, with its band gap tunable from 2.2 to 1.6 eV, depending on the amorphous and crystalline phase. Here we present results from an interlaboratory study on the interplay between the structural change and resulting optical contrast during the amorphous-to-crystalline transformation triggered both thermally and optically. By statistical analysis of Raman and ellipsometric spectroscopic data, we have identified two regimes of crystallization, namely 250°C ≤ T < 300°C, resulting in Type-I spherulitic crystallization yielding an optical contrast Δn ∼ 0.4, and 300 ≤ T < 350°C, yielding Type-II crystallization bended spherulitic structure with different dielectric function and optical contrast Δn ∼ 0.2 below 1.5 eV. Based on our findings, applications of on-chip reconfigurable nanophotonic phase modulators and of a reconfigurable high-refractive-index core/phase-change shell nanoantenna are designed and proposed.

Towards Real-Time In-Situ Mid-Infrared Spectroscopic Ellipsometry in Polymer Processing.

Recent developments in mid-infrared (MIR) spectroscopic ellipsometry enabled by quantum cascade lasers (QCLs) have resulted in a drastic improvement in signal-to-noise ratio compared to conventional thermal emitter based instrumentation. Thus, it was possible to reduce the acquisition time for high-resolution broadband ellipsometric spectra from multiple hours to less than 1 s. This opens up new possibilities for real-time in-situ ellipsometry in polymer processing. To highlight these evolving capabilities, we demonstrate the benefits of a QCL based MIR ellipsometer by investigating single and multilayered polymer films. The molecular structure and reorientation of a 2.5 µm thin biaxially oriented polyethylene terephthalate film is monitored during a stretching process lasting 24.5 s to illustrate the perspective of ellipsometric measurements in dynamic processes. In addition, a polyethylene/ethylene vinyl alcohol/polyethylene multilayer film is investigated at a continuously varying angle of incidence (0∘- 50∘) in 17.2 s, highlighting an unprecedented sample throughput for the technique of varying angle spectroscopic ellipsometry in the MIR spectral range. The obtained results underline the superior spectral and temporal resolution of QCL ellipsometry and qualify this technique as a suitable method for advanced in-situ monitoring in polymer processing.

Determining the Dielectric Tensor of Microtextured Organic Thin Films by Imaging Mueller Matrix Ellipsometry.

Polycrystalline textured thin films with distinct pleochroism and birefringence comprising oriented rotational domains of the orthorhombic polymorph of an anilino squaraine with isobutyl side chains (SQIB) are analyzed by imaging Mueller matrix ellipsometry to obtain the biaxial dielectric tensor. Simultaneous fitting of transmission and oblique incidence reflection Mueller matrix scans combined with the spatial resolution of an optical microscope allows to accurately determine the full biaxial dielectric tensor from a single crystallographic sample orientation. Oscillator dispersion relations model well the dielectric tensor components. Strong intermolecular interactions cause the real permittivity for all three directions to become strongly negative near the excitonic resonances, which is appealing for nanophotonic applications.