Substrate-integrated Hollow Waveguide Research Articles

Miniaturizing gas sensors combining mid-infrared interband cascade light emitting diodes with substrate-integrated hollow waveguides

In this study, we report a compact and versatile gas sensor system combining mid-infrared interband cascade light emitting diodes (MIR-ICLEDs) with substrate-integrated hollow waveguides (iHWGs) toward miniaturized gas sensors. Two readily exchangeable MIR-ICLEDs with center emission wavelengths of 3.4 µm (2941 cm−1) and 5.7 µm (1754 cm−1), respectively, were integrated into a modular sensor system using the iHWG simultaneously as a miniaturized gas cell. The performance of the sensor system for quantitative analysis was evaluated based on calibration functions established for four analytes (i.e., methane, isobutane, acetone, and acetaldehyde) within the respective spectral regions. The utility of such a sensor system as a non-dispersive infrared sensor was tested for various scenarios, including the application of spectral filters, the performance of the individual ICLEDs, and in the analysis of gas mixtures. Furthermore, we demonstrated that the modularity of the sensor design facilitates flexible adaptation to target gas species and available sample volumes, differentiating individual components within gas mixtures.

Fabrication of Low-Cost Miniaturized Gas Cells via SLA 3D-Printing for UV-Based Gas Sensors.

The use of 3D-printing technology for producing optical devices (i.e., mirrors and waveguides) remains challenging, especially in the UV spectral regime. Gas sensors based on absorbance measurements in the UV region are suitable for determining numerous volatile species in a variety of samples and analytical scenarios. The performance of absorbance-based gas sensors is dependent on the ability of the gas cell to propagate radiation across the absorption path length and facilitate interaction between photons and analytes. In this technical note, we present a 3D-printed substrate-integrated hollow waveguide (iHWG) to be used as a miniaturized and ultralightweight gas cell used in UV gas-sensing schemes. The substrates were fabricated via UV stereolithography and polished, and the light-guiding channel was coated with aluminum for UV reflectivity. This procedure resulted in a surface roughness of 11.2 nm for the reflective coating, yielding a radiation attenuation of 2.25 W/cm2. The 3D-printed iHWG was coupled to a UV light source and a portable USB-connected spectrometer. The sensing device was applied for the quantification of isoprene and acetone, serving as a proof-of-concept study. Detection limits of 0.22 and 0.03% in air were obtained for acetone and isoprene, respectively, with a nearly instantaneous sensor response. The development of portable, low-cost, and ultralightweight UV optical sensors enables their use in a wide range of scenarios ranging from environmental monitoring to clinical/medical applications.

Sensing Liquid- and Gas-Phase Hydrocarbons via Mid-Infrared Broadband Femtosecond Laser Source Spectroscopy.

In this study, we demonstrate the combination of a tunable broadband mid-infrared (MIR) femtosecond laser source separately coupled to a ZnSe crystal horizontal attenuated total reflection (ATR) sensor cell for liquid phase samples and to a substrate-integrated hollow waveguide (iHWG) for gas phase samples. Utilizing this emerging light source technology as an alternative MIR radiation source for Fourier transform infrared (FTIR) spectroscopy opens interesting opportunities for analytical applications. In a first approach, we demonstrate the quantitative analysis of three individual samples, ethanol (liquid), methane (gas), and 2-methyl-1-propene (gas), with limits of detection of 0.3% (ethanol) and 22 ppmv and 74 ppmv (methane and isobutylene), respectively, determined at selected emission wavelengths of the MIR laser source (i.e., 890 cm-1, 1046 and 1305 cm-1). Hence, the applicability of a broadband MIR femtosecond laser source as a bright alternative light source for quantitative analysis via FTIR spectroscopy in various sensing configurations has been demonstrated.

Flexible terahertz gas sensing platform based on substrate-integrated hollow waveguides and an opto-electronic light source.

We report on a flexible platform for molecular sensing in the terahertz range. Merging the well-established technologies of near-infrared electro-optic modulation and photomixing realizes a spectrally adaptable terahertz source, which is combined with a new generation of compact gas cells, so-called substrate-integrated hollow waveguides (iHWGs). iHWGs have been developed in the mid-infrared and provide flexibility in the design of the optical absorption path. Here, we demonstrate its suitability for the terahertz domain by presenting its low propagation losses and by measuring rotational transitions of nitrious oxide (N2O). A fast frequency sideband modulation technique results in substantially reduced measurement times and increased accuracy compared to a standard wavelength tuning method.

Towards miniaturized gas sensors based on substrate-integrated hollow waveguides and interband cascade light emitting diodes

We report the first combination of MIR ICLEDs combined with a substrate-integrated hollow waveguide for gas detection. This combination is a pioneering step toward a new generation of miniaturized and low-cost MIR optical sensing devices.

Reagent-less and sub-minute quantification of sulfite in food samples using substrate-integrated hollow waveguide gas sensors coupled to deep-UV LED

The increasing consumption of processed foods demands the usage of chemical preservatives to ensure freshness and extended shelf life. For this purpose, sodium sulfite and its derivatives have been widely used in a variety of food products to inhibit microbial spoilage and for mitigating oxidative decay. However, the excessive consumption of sulfite may cause health problems, thus requiring rapid and accurate analytical methods for the rapid identification of threshold levels. Conventionally, sulfite is volatilized from food samples by acidification followed by trapping of the gaseous SO2 and determination using a suitable analytical technique. Herein, we propose a yet unprecedented reagent-less approach via direct absorbance measurements of gaseous SO2 at 280 nm after sample acidification. The detection system combines a deep-UV LED and a SiC photodiode with a substrate-integrated hollow waveguide (iHWG) gas cell. Absorbance measurements were performed using a log-ratio amplifier circuitry, resulting in noise levels <0.7 mAU. This innovative concept enabled the determination of sulfite in beverages in the range of 25–1000 mg L−1 with suitable linearity (r2 > 0.99) and an analysis time <30 s. The limit of detection (LOD) was calculated at 14.3 mg L−1 (3σ) with an iHWG providing an optical path length of 75 mm. As a proof of concept, this innovative analytical platform was employed for sulfite quantification in concentrated grape juice, coconut water and beer, with suitable accuracy in terms of recovery (83–117%) and favorable comparison with the official Monier-Williams method. Given the inherent modularity and adaptability of the device concept, we anticipate the application of the proposed analytical platform for the in-situ studies addressing sulfite and other volatilized preservatives in a wide variety of food products with tailorable detectability.

RobustATR: Substrate-Integrated Hollow Waveguide Coupled Infrared Attenuated Total Reflectance Sensors

Small and compact mid-infrared devices are of increasing importance, as there are several applications demanding on-site and real-time measurements in harsh real-world scenarios. The RobustATR, an innovative infrared attenuated total reflectance (IR-ATR) accessory, has been developed and tested with exemplary analytes integrating a single-wavelength Fabry–Pérot quantum cascade laser as light source for testing the feasibility of a potentially miniaturized overall sensor design. Successful direct coupling of the laser radiation via substrate-integrated hollow waveguide (iHWG) coupling elements to the sensor interface could be shown, whereby exemplary analytes of environmental and medical relevance were tested, revealing the future potential for real-world applications.

Silicon substrate-integrated hollow waveguide for miniaturized optical gas sensing

Gas sensors have a wide variety of applications. Among various existing gas sensing technologies, optical gas sensors have outstanding advantages. The development of the Internet of Things and consumer electronics has put stringent requirements on miniaturized gas sensing technology. Here, we demonstrate a chip-scale silicon substrate-integrated hollow waveguide (Si-iHWG) to serve as an optical channel and gas cell in an optical gas sensor. It is fabricated through silicon wafer etching and wafer bonding. The Si-iHWG chip is further assembled with an off-chip light source and detector to build a fully functional compact nondispersive infrared (NDIR) CO 2 sensor. The chip size is 10 mm × 9 mm , and the dimension of the sensor excluding the microcontroller board is 50 mm × 25 mm × 16 mm . This chip solution with compactness, versatility, robustness, and low cost provides a cost-effective platform for miniaturized optical sensing applications ranging from air quality monitoring to consumer electronics.

Innovative Substrate-Integrated Hollow Waveguide Coupled Attenuated Total Reflection Sensors for Quantum Cascade Laser Based Infrared Spectroscopy in Harsh Environments.

An innovative mid-infrared spectroscopic sensor system based on quantum cascade lasers has been developed. The system combines the versatility of substrate-integrated hollow waveguides (IHWGs) with the robustness of attenuated total reflection (ATR) crystals employed as internal reflection waveguides for evanescent field sensing. IHWGs are highly reflective metal structures that propagate infrared (IR) radiation and were used as light pipes for coupling radiation into the ATR waveguide. The combined IHWG-ATR device has been designed such that the utmost stability and robustness of the optical alignment were ensured. This novel assembly enables evanescent field absorption measurements at yet unprecedently harsh conditions, that is, high pressure and temperature. Combining these advantages, this innovative sensor assembly is perfectly suited for taking ATR spectroscopy into the field where the robustness of the assembly and optical alignment is essential.

From Light Pipes to Substrate-Integrated Hollow Waveguides for Gas Sensing: A Review.

Absorption-based spectroscopy in the mid-infrared (MIR) spectral range (i.e., 2.5-25 μm) is an excellent choice for directly sensing trace gas analytes providing discriminatory molecular information due to inherently specific fundamental vibrational, rovibrational, and rotational transitions. Complimentarily, the miniaturization of optical components has aided the utility of optical sensing techniques in a wide variety of application scenarios that demand compact, portable, easy-to-use, and robust analytical platforms yet providing suitable accuracy, sensitivity, and selectivity. While MIR sensing technologies have clearly benefitted from the development of advanced on-chip light sources such as quantum cascade and interband cascade lasers and equally small MIR detectors, less attention has been paid to the development of modular/tailored waveguide technologies reproducibly and reliably interfacing photons with sample molecules in a compact format. In this context, the first generation of a new type of hollow waveguides gas cells-the so-called substrate-integrated hollow waveguides (iHWG)-with unprecedented compact dimensions published by the research team of Mizaikoff and collaborators has led to a paradigm change in optical transducer technology for gas sensors. Features of iHWGs included an adaptable (i.e., designable) well-defined optical path length via the integration of meandered hollow waveguide structures at virtually any desired dimension and geometry into an otherwise planar substrate, a high degree of robustness, compactness, and cost-effectiveness in fabrication. Moreover, only a few hundred microliters of gas samples are required for analysis, resulting in short sample transient times facilitating a real-time monitoring of gaseous species in virtually any concentration range. In this review, we give an overview of recent advancements and achievements since their introduction eight years ago, focusing on the development of iHWG-based mid-infrared sensor technologies. Highlighted applications ranging from clinical diagnostics to environmental and industrial monitoring scenarios will be contrasted by future trends, challenges, and opportunities for the development of next-generation portable optical gas-sensing platforms that take advantage of a modular and tailorable device design.

Monitoring Ozone Using Portable Substrate-Integrated Hollow Waveguide-Based Absorbance Sensors in the Ultraviolet Range.

Ozone is an oxidizing molecule used for disinfecting a wide variety of environments, such as in dental clinics, and has most recently been promoted as a sanitizing agent to prevent coronavirus transmission. The easy access to ozone-generating sources also enables their ubiquitous use. However, exposure to ozone may seriously affect human health by amplifying or inducing respiratory diseases and distress syndromes and has been associated with premature deaths from other diseases. In this scenario, miniaturized, low-cost, and portable optical sensors based on the absorption signature of ozone in the ultraviolet (UV) range of the electromagnetic spectrum are an innovative approach for providing real-time monitoring of gaseous ozone, ensuring the safety of indoor and workplace environments. In this paper, a miniaturized ozone sensor based on the absorption signature of ozone at deep-UV frequencies was developed by integration of so-called substrate-integrated hollow waveguides (iHWG) with a miniaturized ultraviolet lamp and a fiber-optic USB-connected spectrophotometer. The innovative concept of iHWGs facilitates unprecedented compact dimensions with a high degree of flexibility in the optical design of the actual photon absorption path. The proposed device rapidly responded to the presence of ozone (<1 min) and revealed a suitable linearity (r 2 > 0.99) in the evaluated concentration range. The limit of detection was determined at 29.4 ppbv, which renders the device suitable for measurements in the threshold range of the main regulatory agencies. Given the adaptability and modularity of this platform, we anticipate the application of this innovative concept to be equally suitable for the in situ and real-time analysis of other relevant gases providing suitable UV absorption signatures.

Metabolic monitoring via on-line analysis of 13C-enriched carbon dioxide in exhaled mouse breath using substrate-integrated hollow waveguide infrared spectroscopy and luminescence sensing combined with Bayesian sampling

In studies that target specific functions or organs, the response is often overlaid by indirect effects of the intervention on global metabolism. The metabolic side of these interactions can be assessed based on total energy expenditure (TEE) and the contributions of the principal energy sources, carbohydrates, proteins and fat to whole body CO2 production. These parameters can be identified from indirect calorimetry using respiratory oxygen intake and CO2 dioxide production data that are combined with the response of the 13CO2 release in the expired air and the glucose tracer enrichment in plasma following a 13C glucose stable isotope infusion. This concept is applied to a mouse protocol involving anesthesia, mechanical respiration, a disease model, like hemorrhage and therapeutic intervention. It faces challenges caused by a small sample size for both breath and plasma as well as changes in metabolic parameters caused by disease and intervention. Key parameters are derived from multiple measurements, all afflicted with errors that may accumulate leading to unrealistic values. To cope with these challenges, a sensitive on-line breath analysis system based on substrate-integrated hollow waveguide infrared spectroscopy and luminescence (iHWG-IR-LS) was used to monitor gas exchange values. A Bayesian statistical model is developed that uses established equations for indirect calorimetry to predict values for respiratory gas exchange and tracer data that are consistent with the corresponding measurements and also provides statistical error bands for these parameters. With this new methodology, it was possible to estimate important metabolic parameters (respiratory quotient (RQ), relative contribution of carbohydrate, protein and fat oxidation fcarb, ffat and fprot , total energy expenditure TEE) in a resolution never available before for a minimal invasive protocol of mice under anesthesia.

NOx Measurements in Vehicle Exhaust Using Advanced Deep ELM Networks

Considering that vehicle exhaust contributes to the majority of nitrogen oxides (NOx), which is harmful to environment and climate, it is important to measure NOx concentrations in sustainable developments. This article proposes to apply spectroscopic gas sensing methods and an innovative deep learning network algorithm for obtaining high-precision NOx data. The adopted mid-infrared sensor technology is based on mid-infrared spectroscopy combined with an advanced substrate-integrated hollow waveguide (iHWG) sensing interface. Using extreme learning machine (ELM) algorithms with an exceptionally fast learning speed when dealing with big data problems next to excellent generalization abilities, a deep learning network for regressing NOx concentrations was implemented. Moreover, to further improve the regression performance the proposed deep ELM was provided with features derived from supervised learning improving its ability to address target constituents. Finally, experiments with gas mixtures containing three species relevant in exhaust emission monitoring have confirmed the utility of the developed approach.

Characterization of metal oxide gas sensors via optical techniques

Metal oxide (MOX) sensors are increasingly gaining attention in analytical applications. Their fundamental operation principle is based on conversion reactions of selected molecular species at their semiconducting surface. However, the exact turnover of analyte gas in relation to the concentration has not been investigated in detail to date. In the present study, two optical sensing techniques—luminescence quenching for molecular oxygen and infrared spectroscopy for carbon dioxide and methane—have been coupled for characterizing the behavior of an example semiconducting MOX methane gas sensor integrated into a recently developed low-volume gas cell. Thereby, oxygen consumption during MOX operation as well as the generation of carbon dioxide from the methane conversion reaction could be quantitatively monitored. The latter was analyzed via a direct mid-infrared gas sensor system based on substrate-integrated hollow waveguide (iHWG) technology combined with a portable Fourier transform infrared spectrometer, which has been able to not only detect the amount of generated carbon dioxide but also the consumption of methane during MOX operation. Hence, a method based entirely on direct optical detection schemes was developed for characterizing the actual signal generating processes—here for the detection of methane—via MOX sensing devices via near real-time online analysis.Graphical

Towards high-precision hollow waveguide-based gas sensors adapting nonuniform pressure and immune to flow fluctuation

Hollow waveguide (HWG) based gas sensors boast fast response time, high-sensitivity, compactness, but less-precision for their intrinsic very small bore-diameter and sampling volume. We investigated the effects of gas flow regimes on the complicated spectral line broadening in HWGs, and analyzed quantitatively by taking atmospheric water vapor spectrum as an example. We derived an equivalent pressure to simplify the calculation of spectral line broadening in nonuniform pressure of HWGs, and proposed to enhance the performance of such kinds of sensors with wavelength modulation spectroscopy by laminar flow regime, pump down mode, and the optimized flow rate. Experimental results showed dramatic improvements with the scheme: sensitivity increase by 18.6%, lower uncertainty, and immune to flow fluctuation. The method is efficient, convenient and with no extra cost. It can promote both HWG and substrate-integrated HWG (iHWG) based gas sensors.

Sample-Sample Correlation Asynchronous Spectroscopic Method Coupled with Multivariate Curve Resolution-Alternating Least Squares To Analyze Challenging Bilinear Data.

An approach to construct a secondary asynchronous spectrum via sample-sample correlation (SASS) is proposed to analyze bilinear data from hyphenated spectroscopic experiments. In SASS, bilinear data is used to construct a series of two-dimensional (2D) sample-sample correlation spectra. Then a vertical slice is extracted from each 2D sample-sample correlation spectrum so that a secondary 2D asynchronous spectrum is constructed via these slices. The advantage of SASS is demonstrated by a model system with the following challenging situations: (1) Temporal profiles of different components severely overlap, making spectra of pure components difficult to directly obtain from either original bilinear data or multivariate curve resolution-alternating least squares (MCR-ALS) with non-negativity and unimodality constraints. (2) Every peak in the spectra of the eluted samples contains contributions from at least two components. Hence, two-dimensional correlation spectroscopy (2D-COS) and n-dimensional (nD) asynchronous spectroscopic method developed in our previous work, which previously worked so well, are now invalid. SASS managed to reveal different groups of systematic absences of cross peaks (SACPs) that reflect the lack of spectral contributions of different components at different regions in the second asynchronous spectrum. Spectra of different components can still be faithfully retrieved via MCR-ALS calculation using constraints revealed by different groups of SACPs. The results demonstrate that implicit but intrinsic information revealed by SASS is indispensable in solving challenging bilinear data as the model system. We applied SASS on two real-world examples from thermogravimetry-Fourier transform infrared spectroscopy (TG-FT-IR) experiments of mixtures (H2O/HOD/D2O and H2O/isopropanol/pyridine). FT-IR spectra of different components were successfully recovered. Moreover, FT-IR spectrum of HOD, which is difficult to obtain, was successfully extracted. SASS can be applied in the analysis of gaseous mixtures from TG-FT-IR experiment and a combination of quantum cascade lasers with substrate-integrated hollow waveguides in environmental monitoring and biomedical diagnosis. Furthermore, SASS is also useful in various advanced hyphenated spectroscopic experiments.

Optimizing the Analytical Performance of Substrate-Integrated Hollow Waveguides: Experiment and Simulation.

The goal of this technical note was to compare experimentally and via simulation of eight substrate-integrated hollow waveguide (iHWG) designs, and to predict promising future iHWG structures in lieu of experiments. The iHWGs differed in their geometry (i.e., inlet funnel cross-section and inner channel cross-section), as well as in their material properties (i.e., type of metal, polish of inner channel). Experimentally, calibration functions of isobutane as a model analyte were determined, and the analytical figures of merit, i.e., signal-to-noise ratio, limit of detection, were evaluated for each iHWG. Evaluation of the amount of radiation incident at the real-world and simulated detector revealed that experiment and simulation were in excellent agreement. While material and quality of the inner channel wall did not have a significant influence on the performance, the iHWG geometry profoundly affected the performance in terms of light throughput: Increasing the inlet funnel dimensions and the inner channel cross-section benefits light throughout, and thus, the analytical signal. Based on these results, simulations of not yet fabricated iHWGs were performed and promising new iHWG structures were suggested.

IBEAM: substrate-integrated hollow waveguides for efficient laser beam combining.

Laser light sources are routinely applied building blocks in optical sensor technologies. While lasers are emitting at a precisely defined wavelength within narrow emission bands, chem/bio-sensing applications frequently demand multi-wavelength illumination for addressing a series of species. Instead of using broadband radiation sources, it is a viable strategy to efficiently combine the beams emitted from different lasers to maintain the spectral brightness and yet cover extended wavelength regimes. In this study, substrate-integrated hollow waveguides (iHWGs) are reported as a versatile and efficient alternative compared to conventional beam combining concepts, especially for applications in the mid-infrared spectral regime leading to a highly efficient multi-port beam combiner-the iBEAM.

Hybrid Analytical Platform Based on Field-Asymmetric Ion Mobility Spectrometry, Infrared Sensing, and Luminescence-Based Oxygen Sensing for Exhaled Breath Analysis.

The reliable online analysis of volatile compounds in exhaled breath remains a challenge, as a plethora of molecules occur in different concentration ranges (i.e., ppt to %) and need to be detected against an extremely complex background matrix. Although this complexity is commonly addressed by hyphenating a specific analytical technique with appropriate preconcentration and/or preseparation strategies prior to detection, we herein propose the combination of three different detector types based on truly orthogonal measurement principles as an alternative solution: Field-asymmetric ion mobility spectrometry (FAIMS), Fourier-transform infrared (FTIR) spectroscopy-based sensors utilizing substrate-integrated hollow waveguides (iHWG), and luminescence sensing (LS). By carefully aligning the experimental needs and measurement protocols of all three methods, they were successfully integrated into a single compact analytical platform suitable for online measurements. The analytical performance of this prototype system was tested via artificial breath samples containing nitrogen (N2), oxygen (O2), carbon dioxide (CO2), and acetone as a model volatile organic compound (VOC) commonly present in breath. All three target analytes could be detected within their respectively breath-relevant concentration range, i.e., CO2 and O2 at 3-5 % and at ~19.6 %, respectively, while acetone could be detected with LOQs as low as 165-405 ppt. Orthogonality of the three methods operating in concert was clearly proven, which is essential to cover a possibly wide range of detectable analytes. Finally, the remaining challenges toward the implementation of the developed hybrid FAIMS-FTIR-LS system for exhaled breath analysis for metabolic studies in small animal intensive care units are discussed.

Real-Time and Simultaneous Monitoring of NO, NO2, and N2O Using Substrate-Integrated Hollow Waveguides Coupled to a Compact Fourier Transform Infrared (FT-IR) Spectrometer.

Nitrogen-based fertilizers have been used in modern agricultural activities resulting in a relevant emission source of nitrogen gases into the atmosphere, mainly nitric oxide (NO), nitrogen dioxide (NO2), and nitrous oxide (N2O). Furthermore, the burning of fossil fuels is the most significant emission source of NOx (i.e., NO + NO2), being the controlling of vehicle exhaust system an essential task. Those compounds can be related to air pollution effects either directly, by emitting a powerful greenhouse gas (i.e., N2O), or indirectly, by formation of nitric acid (HNO3) or ammonium nitrate (NH4NO3) from NO or NO2, responsible for the increase of acid rain and particulate material into the atmosphere. This context requires appropriate sensor technology facilitating in situ and simultaneous monitoring of nitrogen emitted gases, with easiness of operation and compact dimensions. In this communication, we describe an innovative mid-infrared chemical sensor platform for the in situ, real-time, and simultaneous quantification of gaseous NO, NO2, and N2O by combining a compact Fourier transform infrared (FT-IR) spectrometer with the so-called substrate-integrated hollow waveguide (iHWG) as a miniaturized gas cell. The optical platform enabled limits of detection of 10, 1, and 0.5 ppm of NO, NO2, and N2O, respectively. The linear concentration range evaluated in this study is suitable for the application of the sensing platform in vehicle exhaust air samples. Given the high adaptability of the developed infrared sensing device toward preconcentration or ultraviolet conversion modules and also considering the potential for combining tunable interband cascade lasers (ICLs) in lieu of the FT-IR spectrometer, we anticipate the application of the sensing platform for in situ determination of nitrogen gases in a wide range of scenarios.