Julian Haas

Advances in Mid-Infrared Spectroscopy for Chemical Analysis

Infrared spectroscopy in the 3-20 μm spectral window has evolved from a routine laboratory technique into a state-of-the-art spectroscopy and sensing tool by benefitting from recent progress in increasingly sophisticated spectra acquisition techniques and advanced materials for generating, guiding, and detecting mid-infrared (MIR) radiation. Today, MIR spectroscopy provides molecular information with trace to ultratrace sensitivity, fast data acquisition rates, and high spectral resolution catering to demanding applications in bioanalytics, for example, and to improved routine analysis. In addition to advances in miniaturized device technology without sacrificing analytical performance, selected innovative applications for MIR spectroscopy ranging from process analysis to biotechnology and medical diagnostics are highlighted in this review.

Mid-Infrared Spectroscopy Platform Based on GaAs/AlGaAs Thin-Film Waveguides and Quantum Cascade Lasers

The performance and versatility of GaAs/AlGaAs thin-film waveguide technology in combination with quantum cascade lasers for mid-infrared spectroscopy in comparison to conventional FTIR spectroscopy is presented. Infrared radiation is provided by a quantum cascade laser (QCL) spectrometer comprising four tunable QCLs providing a wavelength range of 5-11 μm (1925-885 cm(-1)) within a single collimated beam. Epitaxially grown GaAs slab waveguides serve as optical transducer for tailored evanescent field absorption analysis. A modular waveguide mounting accessory specifically designed for on-chip thin-film GaAs waveguides is presented serving as a flexible analytical platform in lieu of conventional attenuated total reflection (ATR) crystals uniquely facilitating macroscopic handling and alignment of such microscopic waveguide structures in real-world application scenarios.

Sensing chlorinated hydrocarbons via miniaturized GaAs/AlGaAs thin-film waveguide flow cells coupled to quantum cascade lasers

Mid-infrared (MIR) sensors based on attenuated total reflection (ATR) spectroscopy provide robust, rapid and sensitive platforms for the detection of low levels of organic molecules and pollutants. Nowadays, MIR (3–15 μm) spectroscopy has evolved into a versatile sensing technique providing inherent molecular selectivity for the detection of organic and inorganic molecules. The excitation of vibrational and rotational transitions enables the qualitative and quantitative analysis of molecular constituents in solid, liquid, and vapor phases, which facilitates the application of MIR chem/bio sensors for on-site environmental analysis in scenarios such as trace pollutant monitoring or spill detection. This report presents the first integration of thin-film gallium arsenide/aluminum gallium arsenide (GaAs/AlGaAs) into a miniaturized liquid flow cell designed for continuous trace analysis of chlorinated hydrocarbons (CHCs) in water coupled to a broadly tunable quantum cascade laser (QCL), which facilitates in-field deployment of QCL-based sensing devices ensuring water quality and water safety.

Development of a diamond waveguide sensor for sensitive protein analysis using IR quantum cascade lasers

Microfabricated diamond waveguides, between 5 and 20 μm thick, manufactured by chemical vapor deposition of diamond, followed by standard lithographic techniques and inductively coupled plasma etching of diamond, are used as bio-chemical sensors in the mid infrared domain: 5-11 μm. Infrared light, emitted from a broadly tunable quantum cascade laser with a wavelength resolution smaller than 20 nm, is coupled through the diamond waveguides for attenuated total reflection spectroscopy. The expected advantages of these waveguides are a high sensitivity due to the high number of internal reflections along the propagation direction, a high transmittance in the mid-IR domain, the bio-compatibility of diamond and the possibility of functionalizing the surface layer. The sensor will be used for analyzing different forms of proteins such as α-synuclein which is relevant in understanding the mechanism behind Parkinsons disease. The fabrication process of the waveguide, its characteristics and several geometries are introduced. The optical setup of the biosensor is described and our first measurements on two analytes to demonstrate the principle of the sensing method will be presented. Future use of this sensor includes the functionalization of the diamond waveguide sensor surface to be able to fish out alpha-synuclein from cerebrospinal fluid.

Polycrystalline Diamond Thin-Film Waveguides for Mid-Infrared Evanescent Field Sensors

Photonic design and optimization of thin-film polycrystalline diamond waveguides are shown, serving as advanced evanescent field transducers in the mid-infrared fingerprint regime (2000–909 cm–1; 5–11 μm). Design constraints inherent to optical/system considerations and the material were implemented in a finite element method (FEM)-based simulation method that allowed three-dimensional modeling of the overall structure. Thus, lateral mode confinement, attenuation in the direction of radiation propagation, and physical resilience were evaluated. In a final step, the designed structures were fabricated, and their utility in combination with a broadly tunable external cavity quantum cascade laser for chemical sensing of a liquid phase analyte was demonstrated.

Plasmonic nanostars as signal enhancers for surface-enhanced vibrational spectroscopy and optical imaging (Conference Presentation)

Plasmonic gold nanostars (NSts) demonstrate an enhanced electric field in their surrounding due to large number of ‘hot spots’ on their surface resulting in a unique ability to confine light within a nanometric volume. We are demonstrating beneficial properties of NSts as signal enhancers for tissue and cell imaging using optical coherence tomography (OCT), microscopy, surface-enhanced vibration spectroscopy (SEVS), including surface-enhanced Raman scattering (SERS), and surface-enhanced infrared absorption spectroscopy (SEIRAS) with an attenuated total reflectance (ATR) and infrared reflection-absorption spectroscopy (IRRAS) configurations. Scattering ability of gold NSts with various sizes was investigated by OCT capillary imaging and light and confocal microscopy in vitro. The variation of NSts sizes allows one to shift plasmon resonance up to 1300 nm. The most intensive scattering signals were found from the largest NSts. NSts were applied in SEVS scenarios using plasmonic chip-based systems containing self-assembled NSts on a silicon substrate both by evaporation and subsequent immobilization mediated by a gold layer and modified-dimercapto polyethylene glycol. The plasmonic substrates are able to concomitantly enhance Raman and mid-infrared signals. SERS and SEIRAS properties of such substrates were demonstrated. For SERS, by using crystal violet as a model analyte. The IR absorbance of analyte molecules placed on NSt-film deposited on a Si ATR crystal was up to 10 times higher for thioglycolic acid and 2 times higher for bovine serum albumin compared to a bare Si waveguide. For the best of our knowledge, this is the first attempt to use NSt-based substrate for SEIRAS studies.

polyHWG: 3D Printed Substrate-Integrated Hollow Waveguides for Mid-Infrared Gas Sensing

Gas analysis via mid-infrared (MIR) spectroscopic techniques has gained significance due to its inherent molecular selectivity and sensitivity probing pronounced vibrational, rotational, and roto-vibrational modes. In addition, MIR gas sensors are suitable for real-time monitoring in a wide variety of sensing scenarios. Our research team has recently introduced so-called substrate-integrated hollow waveguides (iHWGs) fabricated by precision milling, which have been demonstrated to be useful in online process monitoring, environmental sensing, and exhaled breath analysis especially if low sample volumes (i.e., few hundreds of microliters) are probed with rapid signal transients. A logical next step is to establish ultralightweight, potentially disposable, and low-cost substrate-integrated hollow waveguides, which may be readily customized and tailored to specific applications using 3D printing techniques. 3D printing provides access to an unprecedented variety of thermoplastic materials including biocompatible polylactides, readily etchable styrene copolymers, and magnetic or conductive materials. Thus, the properties of the waveguide may be adapted to suit its designated application, e.g., drone-mounted ultralightweight waveguides for environmental monitoring or biocompatible disposable sensor interfaces in medical/clinical applications.