Achim Voigt

Plasma regeneration was investigated as a means of regenerating microstructures on biosensors for repeated use. These microstructures were based on the deposition of suspensions containing polymer microspheres. While this method provides a simple way to structure surfaces, obtaining regular structures in a reproducible way remains a challenge. Therefore, it would be advantageous to be able to reuse regular structures, which requires regeneration. To investigate this concept, surface acoustic wave (SAW) resonators were structured using 5 µm and 20 µm polystyrene microspheres and coated with parylene C to stabilize the particle structures. After use in bioanalytical experiments, the biological residues and the parylene C cover layer were removed with plasma, and a new parylene C layer was added. Both atmospheric and low-pressure plasma were tested for regeneration. As a result, the low-pressure plasma was to be preferred because it did not damage the transducer structures on the SAW resonators, unlike the atmospheric plasma. Water contact angle measurements and transmission spectra recorded with a network analyzer confirmed that freshly prepared and regenerated structured SAW resonators coated with parylene C exhibited similar wetting properties and resonance parameters. Therefore, plasma regeneration is an effective way to enable the reuse of perfectly structured SAW resonators.

The technology of surface acoustic wave-based (SAW) sensors greatly depends on the performance of the resulting sensing layer. To ensure real applications, the sensors must be produced with reproducibility, as well as the statistical consistency of analytical sensor response results must be assured. In this work, we investigated the reproducibility and the statistical performance of the coating procedure used in previous works for the development of new polymeric coating materials, and the statistics of the respective sensor responses were analyzed. The polylaurylmethacrilate (PLMA) is used as an example of polymeric coating material. Two series of sensors coated with distinct quantities of the polymer were produced and analyzed. The statistical analysis of the ultrasonic parameters of the sensor production presented very low variability for both series of sensors. The respective sensor responses, obtained with a set of analytes with distinct chemical functions, presented, in the same way, excellent reproducibility for both series of sensors. The very good reproducibility and statistical robustness of the sensor production data and of the respective sensor responses confirm the reliability of the methodology to produce sensors for the SAW technology.

Surface acoustic wave-based (SAW) sensors are of great interest due to their high sensibility and fast and stable responses. They can be obtained at an overall low cost and with an intuitive and easy-to-use method. The chemical sensitization of a piezoelectric transducer plays a key role in defining the properties of SAW sensors. In this study, we investigate the structural and adhesion properties of a new class of coating material based on polyurethane polymeric composites. We used dark-field microscopy (DFM) and scanning electron microscopy (SEM) to observe the microstructure of polyurethane composite coatings on piezoelectric sensor elements and to analyze the effects of the chemical resistance and adhesion test (CAT) on the coating layers obtained with the polyurethane polymeric composites. The results of the microscopy showed that all polyurethane composite coatings exhibited excellent uniformity and stability after chemical adherence testing (CAT). All of the observations were correlated with the results of the ultrasonic analysis, which demonstrated the role of polyurethane as a binder to form the stable structure of the composites and, at the same time, as an adhesion promoter, increasing the chemical resistance and the adherence of the coating layer to the complex surface of the piezoelectric sensor element.

The chemical sensitization of surface acoustic wave (SAW) sensors plays a key role for this technology. The analysis of the resulting nanometric sensing layer is crucial for the development of new sensing materials as well as for the quality control of SAW sensors systems for commercial applications. In the previous works, the resulting coating layers using new coating materials based on polyurethane-polymer composites were evaluated considering the ultrasonic analysis, the adhesion, and the sensor responses. In this work, the characterization of the coating process, Bright Field Microscopy (BFM) and Dark Field Microscopy (DFM) were used to evaluate the quality of the material distribution and homogeneity of the obtained sensing layers. The sensing materials analyzed were the four polymers used in the previous works and their respective new composites with polyurethane (PU). The combination of BFM and DFM allows the characterization of the resulting material distribution obtained by the coating process, providing inferences about the interaction of each coating material with the surface of the SAW sensor element as well as about the correlation between the results of the ultrasonic parameters, the real material distribution and the homogeneity of the obtained coating layer of each coating material.

This work presents the application of the methodology for the sensitization of surface acoustic wave-based sensors (SAW), developed in the first part of this work. The strategy of the method is the obtention of sensing layers with tailored chemical environments by taking advantage of the wide variety of chemical composition of the organic polymers, which have been used as sensing polymers, and combining them with polyurethane (PU) to form polymeric composites that show enhanced properties as sensing materials for the SAW sensor technology. In the first part of this work, the ultrasonic and adhesion characterization was correlated to the sensor responses of PU-polybutylmethacrylate (PBMA) composites of different relative concentrations of the sensing polymer (PBMA) and PU. The resulting coating layers obtained with the PU polymer composites improved the chemical and mechanical properties of the sensing layer without interfering with the quality of their sensor responses in comparison to those with the pristine polymer as the sensing material. In this second part of this work, three new polyurethane polymeric composites were analyzed. The new sensing materials were produced using polylaurylmetacrylate (PLMA), polyisobutene (PIB), and poly(chlorotrifluoroethylene-co-vinylidene fluoride) (PCTFE) as the sensing polymers combined with PU. The results of the new PU polymer composites showed consequently different properties depending on the type of sensing polymer used, reproducing, however, the previous features achieved with PU and polybutylmetacrylate (PBMA) composites, like the improvements in the adhesion and the resistance against an organic solvent and preserving, in each case, the sensor response characteristic of each sensing polymer used, as was also observed for the PU-PBMA polymeric composites. The results obtained with the new sensing materials validated the strategy and confirmed its generalization as a very suitable methodology for the sensitization of SAW sensors, strongly indicating the applicability and reliability of the method, which makes possible the choice of virtually any chemical environments for the sensitization of SAW sensor systems.

A surface acoustic wave (SAW) resonator chip setup is presented that eliminates interfering signal responses caused by changes in the electrical environment of the surrounding media. When using a two-port resonator, applying electrically shielding layers between the interdigital transducers (IDTs) can be challenging due to the limited dimensions. Therefore, a layered setup consisting of an insulating polymer layer and a conductive gold layer was preferred. The SAW resonators were provided with polycarbonate housings, resulting in SAW resonator chips. This setup enables easy application of a wide range of coatings to the active part of the resonator surface, while ensuring subsequent electrical and fluidic integration of the resonator chips into a microfluidic array for measurements. The signal responses of uncoated SAW resonators and those with polymer coatings with and without a gold layer were tested with aqueous potassium chloride (KCl) solutions up to 3 mol/L, corresponding to conductivities up to 308 mS/cm. The use of a polymer coating at the thickness of the first Love mode resonance and a conductive gold layer completely reduced the electrical impact on the SAW resonator signal response, making small signals resulting from changes in viscosity and density of the KCl solutions visible.

The sensing layers for surface acoustic wave-based (SAW) sensors are the main factor in defining the selectivity and reproducibility of the responses of the sensor systems. Among the materials used as sensing layers for SAW sensors, polymers present a wide range of advantages, from availability to a large choice of chemical-sensing environments. However, depending on the physical–chemical properties of the polymer, issues about the chemical and mechanical stability of the sensing layer have been reported that can compromise the application of sensor systems in the long-term. The sensor properties are defined basically by the properties of the coating material and the quality of the coating process. The strategy used to improve the properties of polymeric coating layers for SAW technology involved the use of polyurethane (PU) in combination with a second polymer that is responsible for the sensing properties of the resulting layer; this is obtained by a reproducible and robust coating procedure. In this first part of our research, we used polymer composites of different compositions of polybutylmetacrylate (PBMA) as the sensing polymer with polyurethane. The analysis of the coating (ultrasonic parameters), the relative sensor responses and the adhesion results for the PU–PBMA composites were determined. The ultrasonic analysis and the relative sensor responses showed very reproducible and precise results, indicating the reproducibility and robustness of the coating process. Accurate correlations between the results of the ultrasonic parameters due to the coating and the relative sensor responses for the organic analytes analyzed were obtained, showing a precise quantitative relationship between the results and the constitution of the composite coating materials. The composites show practically no significant sensor responses to water. The PU–PBMA composites substantially enhanced adhesion to the surface of the piezoelectric sensor element in comparison to the coating with pure PBMA, without loss of its sensing properties. Other PU–polymer composites will be presented in the future, as well as an analysis of the selectivity for the organic analytes for these types of coating materials.

A self-developed and newly re-designed chemical SAW sensor system composed of four polymer-coated and four differently modified nano-diamond-coated SAW sensors was applied to measure aromatic compounds in gasoline in a low-cost, fast, and easy way. An additional short packed column at the system inlet improve the selectivity for various possible fuel applications. The column allows the direct sampling of liquid fuels and pre-separates the different components in groups (aromatic and aliphatic compounds) from a fuel sample. Since the sensors employed show linearity towards concentration, an easy quantification of single fuel components was possible even within the group of aromatic compounds.

A microfluidic chip for electrochemical impedance spectroscopy (EIS) is presented as bio-sensor for label-free detection of proteins by using the example of cardiac troponin I. Troponin I is one of the most specific diagnostic serum biomarkers for myocardial infarction. The microfluidic impedance biosensor chip presented here consists of a microscope glass slide serving as base plate, sputtered electrodes, and a polydimethylsiloxane (PDMS) microchannel. Electrode functionalization protocols were developed considering a possible charge transfer through the sensing layer, in addition to analyte-specific binding by corresponding antibodies and reduction of nonspecific protein adsorption to prevent false-positive signals. Reagents tested for self-assembled monolayers (SAMs) on gold electrodes included thiolated hydrocarbons and thiolated oligonucleotides, where SAMs based on the latter showed a better performance. The corresponding antibody was covalently coupled on the SAM using carbodiimide chemistry. Sampling and measurement took only a few minutes. Application of a human serum albumin (HSA) sample, 1000 ng/mL, led to negligible impedance changes, while application of a troponin I sample, 1 ng/mL, led to a significant shift in the Nyquist plot. The results are promising regarding specific detection of clinically relevant concentrations of biomarkers, such as cardiac markers, with the newly developed microfluidic impedance biosensor chip.

A prototype of a wireless vacuum microsensor combining the Pirani principle and surface acoustic waves (SAW) with extended range and sensitivity was designed, modelled, manufactured and characterised under different conditions. The main components of the prototype are a sensing SAW chip, a heating coil and an interrogation antenna. All the components were assembled on a 15 mm × 11 mm × 3 mm printed circuit board (PCB). The behaviour of the PCB was characterised under ambient conditions and in vacuum. The quality of the SAW interrogation signal, the frequency shift and the received current of the coil were measured for different configurations. Pressures between 0.9 and 100,000 Pa were detected with sensitivities between 2.8 GHz/Pa at 0.9 Pa and 1 Hz/Pa close to atmospheric pressure. This experiment allowed us to determine the optimal operating conditions of the sensor and the integration conditions inside a vacuum chamber in addition to obtaining a pressure-dependent signal.