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Towards ultrasensitive SPR-based sensing: self-referencing and detection of single nanoparticles
(2018)
Surface plasmon resonance (SPR) and its extensions, surface plasmon resonance imaging (SPRi) and surface plasmon resonance microscopy (SPRM) both enabling visualization of the sensor surface, belong to classical, indispensable highly sensitive and robust optical (bio)analytical techniques to study affinity processes on a surface. Nevertheless, SPR and SPRi/SPRM undergo a continuous development in regard to the improvement of sensitivity. The main challenge in this direction is attributed to the separation of signals due to the binding of analytes and those due to the bulk effect. The main task of the present thesis was to apply different strategies to improve the performance of SPR sensing. Within this scope, two main objectives were pursued: (1) implementation and realization of a so-called internal referencing towards suppression of the bulk effect leading to an improvement and optimization of the signal-to-noise ratio (SNR) and (2) application of wide-field (WF)-SPRM to detect, to visualize and to characterize single nanoparticles adsorbed to modified surfaces. The first objective of this thesis comprises the realization of three different internal-referencing approaches. In the first approach, a self-referencing effect based on arbitrarily distributed micro-patterned self-assembled monolayer (SAM) containing sensing and referencing spots was realized. Measurements of classical antigen-antibody-interaction resulted in a 10-fold improvement of the SNR by suppression of the bulk effect and the corresponding microfluctuations of the bulk temperature. The application of the second internal-referencing-approach, ionic referencing, acting as an assessment of patterned SAM was realized using electrolytes with a high molar refraction of either anions or cations to micro-patterned SAM combined with WF-SPRM as detecting technology. As a result, successful, unobtrusive visualization and spatial distinction of micro-patterned surfaces was shown. Unlike visualization of micro-scaled surface areas, the application of spatio-temporal referencing in WF-SPRM, as a third type of internal referencing, enables to detect, moreover to visualize and localize, smallest changes in refractive index near/on the sensor surface. In that sense, the second objective of this thesis was dedicated to the application of the WF-SPRM technology combined with spatio-temporal referencing to detect, to visualize, to quantify and to characterize single nanoparticles adsorbed to the sensor surface; here, nanoparticles act as analyte species. Based on a sophisticated image analysis, successful detection and characterization of single nanoparticles in complex media such as wine, juice and sun cream was performed. Besides being a powerful solution for nanoparticles analytics, the WF-SPRM technology represents a base to develop novel, ultra-sensitive and fast (bio)sensing platforms. Within this scope, enzyme-assisted generation of nanoparticles was studied.
The phenomenon of laser-induced periodic surface structures (LIPSS), or ripples, generated by near-infrared radiation with the central wavelength around 800 nanometer (λlaser ≈ 800 nm) and pulse duration about of 100 femtosecond (τpulse ≈ 100 fs) on solid targets is considered in this dissertation. The main aim of the work is a better understanding of the fundamental processes of laser-matter interaction resulting in pattern formation by femtosecond (fs) laser ablation. The problem is of great interest both in fundamental and applied science. The knowledge of the underlying physical mechanisms will provide the opportunity to control surface nanostructuring, which has a big application potential in many modern technologies. Femtosecond LIPSS observed at the bottom of ablation crater reveal a large variety of features including nanostructures with periods below 100 nm. Moreover, the ripple size depends mainly on the irradiation dose/absorbed laser energy and is rather insensitive to the variation of laser wavelength or incidence angle. The orientation of the structures is dictated by laser polarization. All these experimental observations and an astounding similarity of the structures to other patterns originating from instabilities led to the idea to attribute the femtosecond laser nanostructuring to a self-organized pattern formation from laser-induced surface instability. In this dissertation, surface pattern formation upon femtosecond laser ablation is considered in the framework of an adopted surface erosion model, based on the description of spontaneous pattern formation on surfaces bombarded with high-energy ions. We exploit the similarity to ion-beam sputtering and extend a corresponding model for laser ablation by including laser polarization. It has been found that an asymmetry in the deposition and dissipation of the incident laser energy, related to the laser polarization, results in a corresponding dependence of coefficients in a nonlinear equation of the Kuramoto-Sivashinsky type. The surface morphologies calculated in the framework of this model for different configurations of the incident laser electric field show an excellent qualitative agreement with structures observed in ultra-short pulse ablation experiments. In this work, properties of the periodic surface structures induced upon femtosecond laser ablation are studied in detail, focusing on a systematic investigation of the main control parameters regulating the pattern formation process. The results support the non-linear self-organization mechanism of pattern formation from laser-induced surface instability.
This thesis addresses fundamental physical processes which take place at the surface region of a target during and after the interaction with ultra-short laser pulses. The general goal is to bring together different phenomena and discuss the non-equilibrium nature of the interaction of femtosecond laser pulses (tp < 100 fs) with various materials, in particular dielectrics and semiconductors. Different experiments, using various techniques, are designed to explore the basic mechanisms of laser ionization, defect creation, electron-lattice energetic transfer, charged particles desorption, optical breakdown, phase transformations and surface morphological changes. Such processes are shown to depend strongly on the laser intensity. Thus, they are analyzed for intensities over four orders of magnitude (10^11-10^14 W/cm2), around the surface optical breakdown (damage) threshold intensity. First, experimental studies using time-of-flight mass spectrometry indicate that non-resonant intense ultra-short laser pulses can efficiently ionize a dielectric (semiconducting) material leading to emission of electrons as well as charged particles, i.e. atomic ions and large clusters, and neutral particles. Under these irradiation conditions, the ionization processes can be at best described by multiphoton ionization and ionization at defects sites. The structural defects provide the means for an increased positive ion desorption rate. A multiple pulse incubation effect in the ion yield can be well related with the reduction of the multi-pulse damage threshold with increasing intensity. Following the initial electron excitation and emission, positive ions are released from the surface in a substantial amount with high ion velocities indicative of a localized microscopic electrostatic expulsion. With increasing intensity, the amount of ions gets larger and larger and their velocity distribution exhibits a bimodal structure. Also, in these conditions, negative ions are detected. The ion desorption can arise from a combination of a localized electrostatic repulsion (macroscopic Coulomb explosion) and a thermal ‘explosive’ mechanism. The later becomes more important with increasing intensity. The very fast energy input and particle emission result in a transient perturbation and deformation of the target lattice. Using pump-probe experiments the temporal evolution of lattice dynamics can be analyzed upon single-pulse excitation for many different target materials. This deformation is indicated to be a material characteristic. It is associated with the generation of transient defects in dielectrics or fast phase transitions in semiconductors and metals. Therefore, it could well give estimates of lifetime of transient defect states or electron-phonon relaxation times.At last the surface morphology after ablation is analyzed, with emphasis on the laser-induced surface periodic patterns (ripples). The patterns observed appear to be very different from the ‘classical’ ripples formed after long pulse ablation. They can have periods much smaller than the incident wavelength and are rather insensitive to the variation of the laser wavelength and angle of incidence. We show that control factors are laser beam polarization and the irradiation dose. Additionally, the patterns exhibit features pointing toward a chaotic origin. Their possible formation mechanism is likely linked with the non-equilibrium nature of the interaction.