A disposable optofluidic micro-transmission cell with tailorable length for Fourier-transform infrared spectroscopy of biological fluids.

Mid-infrared Fourier-transform infrared (FT-IR) spectroscopy of liquid biological samples is limited by the high absorption of water in this spectral range, which makes conventional transmission cuvettes unsuitable as their centimeter-scale length is already too big. The most common alternative relies on the use of attenuated total reflection (ATR) accessories, which provide a small interaction path length for light along the interface between the analyte and the expensive ATR crystals. In this work, we address this issue by proposing a disposable and low-cost micro-transmission cell. Its construction relies on a simple technique, which consists of dispersing plastic spherical microparticles in a liquid sample before dispensing it between two pieces of silicon assembled one onto the other and acting as windows for the cell. Consequently, the microparticles act as a spacer of very precise height in-between the two silicon windows. This technique allows easy construction of infrared absorption cells with near-optimum optical interaction path length just by selecting the most appropriate particle size. The concept is demonstrated by measuring the concentration of glucose in aqueous solutions using microspheres of diameter 20 µm then 40 µm and analyzing the corresponding glucose absorption peaks in the wavenumber range 950-1200 cm-1. The performance is compared to that of standard ATR spectroscopy of the same samples. This resulted in a root-mean-square error of cross-validation (RMSECV) of 58.8 mg dl-1 as obtained for transmission measurements by partial least squares (PLS) regression, which is comparable to the RMSECV of 53 mg dl-1 for single-reflection diamond ATR measurements.

Single Infrared Spectrum Enables Simultaneous Identification of (Bio)Chemical Nature and Particle Size of Microorganisms and Synthetic Microplastic Beads.

Populations of nearly identical chemical and biological microparticles include the synthetic microbeads used in cosmetic, biomedical, agri-food, and pharmaceutical industries as well as the class of living microorganisms such as yeast, pollen, and biological cells. Herein, we identify simultaneously the size and chemical nature of spherical microparticle populations with diameters larger than 1 µm. Our analysis relies on the extraction of both physical and chemical signatures from the same optical spectrum recorded using attenuated total reflection (ATR)-Fourier transform infrared (FTIR) spectroscopy. These signatures are the spectral resonances caused by the microparticles, which depend on their size and the absorption peaks revealing their chemical nature. We validate the method first on separated and mixed groups of spherical microplastic particles of two different diameters, where the method is used to calculate the diameter of the microspherical particles. Then, we apply the method to correctly identify and measure the diameter of Saccharomyces cerevisiae yeast cells. Theoretical simulations to help in understanding the effect of size distribution and dispersion support our results.

Potential of a Miniature Spectral Analyzer for District-Scale Monitoring of Multiple Gaseous Air Pollutants.

Gas sensors that can measure multiple pollutants simultaneously are highly desirable for on-site air pollution monitoring at various scales, both indoor and outdoor. Herein, we introduce a low-cost multi-parameter gas analyzer capable of monitoring multiple gaseous pollutants simultaneously, thus allowing for true analytical measurement. It is a spectral sensor consisting of a Fourier-transform infrared (FTIR) gas analyzer based on a mid-infrared (MIR) spectrometer. The sensor is as small as 7 × 5 × 2.5 cm3. It was deployed in an open-path configuration within a district-scale climatic chamber (Sense City, Marne-la-Vallée, France) with a volume of 20 × 20 × 8 m3. The setup included a transmitter and a receiver separated by 38 m to enable representative measurements of the entire district domain. We used a car inside the climatic chamber, turning the engine on and off to create time sequences of a pollution source. The results showed that carbon dioxide (CO2) and water vapor (H2O) were accurately monitored using the spectral sensor, with agreement with the reference analyzers used to record the pollution levels near the car exhaust. Furthermore, the lower detection limits of CO, NO2 and NO were assessed, demonstrating the capability of the sensor to detect these pollutants. Additionally, a preliminary evaluation of the potential of the spectral sensor to screen multiple volatile organic compounds (VOCs) was conducted at the laboratory scale. Overall, the results demonstrated the potential of the proposed multi-parameter spectral gas sensor in on-site gaseous pollution monitoring.

Polarized light diffuse reflectance FT-NIR MEMS spectrometer enabling the detection of powder samples through a thin plastic layer.

Polarized scattered light Fourier transform infrared (FTIR) spectroscopy is used for measuring the absorbance of highly scattering materials overcoming the multiple scattering effect. It has been reported for in vivo for biomedical applications and in-field for agricultural and for environmental monitoring. In this paper, we report a polarized light microelectromechanical system (MEMS)-based FTIR in the extended near infrared (NIR) that utilizes a bistate polarizer in a diffuse reflectance measurement setup. The spectrometer is capable of distinguishing between single backscattering from the uppermost layer and multiple scattering from the deep layers. The spectrometer has a spectral resolution of 64c m -1 (about 16 nm at a wavelength of 1550 nm) and operates in the spectral range of 4347c m -1 to 7692c m -1 (1300 nm to 2300 nm). The technique implies de-embedding of the MEMS spectrometer polarization response by normalizing its effect; this is applied on three different samples: milk powder, sugar, and flour in plastic bags. The technique is examined on different scattering size particles. The scattering particles diameter's range is expected to vary from 10 µm to 400 µm. The absorbance spectra of the samples are extracted and compared to the direct diffuse reflectance measurements of the samples, showing good agreement. By using the proposed technique, the calculated error for the flour was decreased from 43.2% to 2.9% at 1935 nm wavelength. The wavelength error dependence is also reduced.

Allan Variance Characterization of Compact Fourier Transform Infrared Spectrometers.

Handheld Fourier transform infrared (FT-IR) spectrometers are very promising candidates for several applications where accurate real-time material detection and quantification are needed. Due to their compact size, their mode of operation which does not allow for long warm-up time, and changing environmental conditions, these spectrometers suffer from short-term noise and long-term instabilities which affect their performance. In this work, the effect of long-term multiplicative instabilities on the signal-to-noise ratio (S/N), measured using the 100% line-method, is studied. An expression for the variance, in this case, is deduced. The Allan variance technique is used to identify and quantify the presence of the different types of noises. The methodology is applied to a commercial NeoSpectra scanner module from Si-Ware Systems, Inc.

Substrate Signal Inhibition in Raman Analysis of Microplastic Particles.

In Raman analysis, the substrate material serves very often for signal enhancement, especially when metallic surfaces are involved; however, in other cases, the substrate has an opposite effect as it is the source of a parasitic signal preventing the observation of the sample material of interest. This is particularly true with the advent of microfluidic devices involving either silicon or polymer surfaces. On the other hand, in a vast majority of Raman experiments, the analysis is made on a horizontal support holding the sample of interest. In our paper, we report that a simple tilting of the supporting substrate, in this case, silicon, can drastically decrease and eventually inhibit the Raman signal of the substrate material, leading to an easier observation of the target analyte of the sample, in this case, microplastic particles. This effect is very pronounced especially when looking for tiny particles. Explanation of this trend is provided thanks to a supporting experiment and further numerical simulations that suggest that the lensing effect of the particles plays an important role. These findings may be useful for Raman analysis of other microscale particles having curved shapes, including biological cells.

Detection of Sub-20 µm Microplastic Particles by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy and Comparison with Raman Spectroscopy.

Microplastics are particulate water contaminants that are raising concerns regarding their environmental and health impacts. Optical spectroscopy is the gold standard for their detection; however, it has severe limitations such as tens of hours of analysis time and spatial resolution of more than 10 µm, when targeting the production of a 2D map of the microparticle population. In this work, through a single spectrum acquisition, we aim at quickly getting information about the whole population of identical particles, their chemical nature, and their size in a range below 20 µm. To this end, we built a compact setup enabling both attenuated total reflection Fourier transform infrared (ATR-FTIR) and Raman spectroscopy measurement on the same sample for comparison purposes. We used monodisperse polystyrene and poly(methyl methacrylate) microplastic spheres of sizes ranging between 6 and 20 µm, also measured collectively using a bench-top FTIR spectrometer in ATR mode. The ATR-FTIR technique appears to be more sensitive for the smallest particles of 6 µm, while the opposite trend is observed using Raman spectroscopy. We use theoretical modeling to simulate and explain the ripples observed in the measured spectra at the shortest wavelength (higher wavenumber) region, which appears as an indicator of the microparticle dimension. The latter finding opens new perspectives for ATR-FTIR for the identification and classification of populations of nearly identical micro-scale bodies, such as bacteria and other micro-organisms, where the same measured spectrum embeds dual information about the chemical nature and the size.

Complex Kernel-based spectrum reconstruction algorithm for cascaded Fabry-Perot interferometric spectrometer.

A method to calculate the spectrum of the light incident on a cascaded Fabry-Perot interferometric spectrometer from the detector signal versus the scanning mirror position is presented. The method is based on modifying the Fabry-Perot integral equation to reduce possible spectrum reconstruction errors that arise due to inaccurate determination of the optical path difference reference position and the dependence on the dispersion of the cavity material. A transformation algorithm that employs the suggested kernel modification is derived and tested. The presented algorithm is then compared to the conventional kernel, showing spectral error reductions by larger than 20 dB.

Spatiotemporal dynamics of nanowire growth in a microfluidic reactor.

Co-integration of nanomaterials into microdevices poses several technological challenges and presents numerous scientific opportunities that have been addressed in this paper by integrating zinc oxide nanowires (ZnO-NWs) into a microfluidic chamber. In addition to the applications of these combined materials, this work focuses on the study of the growth dynamics and uniformity of nanomaterials in a tiny microfluidic reactor environment. A unique experimental platform was built through the integration of a noninvasive optical characterization technique with the microfluidic reactor. This platform allowed the unprecedented demonstration of time-resolved and spatially resolved monitoring of the in situ growth of NWs, in which the chemicals were continuously fed into the microfluidic reactor. The platform was also used to assess the uniformity of NWs grown quickly in a 10-mm-wide microchamber, which was intentionally chosen to be 20 times wider than those used in previous attempts because it can accommodate applications requiring a large surface of interaction while still taking advantage of submillimeter height. Further observations included the effects of varying the flow rate on the NW diameter and length in addition to a synergetic effect of continuous renewal of the growth solution and the confined environment of the chemical reaction.

A microfluidic chip enables fast analysis of water microplastics by optical spectroscopy.

Microplastics contaminating drinking water is a growing issue that has been the focus of a few recent studies, where a major bottleneck is the time-consuming analysis. In this work, a micro-optofluidic platform is proposed for fast quantification of microplastic particles, the identification of their chemical nature and size, especially in the 1-100 µm size range. Micro-reservoirs ahead of micro-filters are designed to accumulate all trapped solid particles in an ultra-compact area, which enables fast imaging and optical spectroscopy to determine the plastic nature and type. Furthermore, passive size sorting is implemented for splitting the particles according to their size range in different reservoirs. Besides, flow cytometry is used as a reference method for retrieving the size distribution of samples, where chemical nature information is lost. The proof of concept of the micro-optofluidic platform is validated using model samples where standard plastic particles of different size and chemical nature are mixed.

Silicon Multi-Pass Gas Cell for Chip-Scale Gas Analysis by Absorption Spectroscopy.

Semiconductor and micro-electromechanical system (MEMS) technologies have been already proved as strong solutions for producing miniaturized optical spectrometers, light sources and photodetectors. However, the implementation of optical absorption spectroscopy for in-situ gas analysis requires further integration of a gas cell using the same technologies towards full integration of a complete gas analysis system-on-chip. Here, we propose design guidelines and experimental validation of a gas cell fabricated using MEMS technology. The architecture is based on a circular multi-pass gas cell in a miniaturized form. Simulation results based on the proposed modeling scheme helps in determining the optimum dimensions of the gas cell, given the constraints of micro-fabrication. The carbon dioxide spectral signature is successfully measured using the proposed integrated multi-pass gas cell coupled with a MEMS-based spectrometer.

Continuous Monitoring of Air Purification: A Study on Volatile Organic Compounds in a Gas Cell.

Air pollution is one of the major environmental issues that humanity is facing. Considering Indoor Air Quality (IAQ), Volatile Organic Compounds (VOCs) are among the most harmful gases that need to be detected, but also need to be eliminated using air purification technologies. In this work, we tackle both problems simultaneously by introducing an experimental setup enabling continuous measurement of the VOCs by online absorption spectroscopy using a MEMS-based Fourier Transform infrared (FTIR) spectrometer, while those VOCs are continuously eliminated by continuous adsorption and photocatalysis, using zinc oxide nanowires (ZnO-NWs). The proposed setup enabled a preliminary study of the mechanisms involved in the purification process of acetone and toluene, taken as two different VOCs, also typical of those that can be found in tobacco smoke. Our experiments revealed very different behaviors for those two gases. An elimination ratio of 63% in 3 h was achieved for toluene, while it was only 14% for acetone under same conditions. Adsorption to the nanowires appears as the dominant mechanism for the acetone, while photocatalysis is dominant in case of the toluene.

Rapid assessment of nanomaterial homogeneity reveals crosswise structural gradients in zinc-oxide nanowire arrays.

In an effort to scale-up nanomaterial growth over large surface areas, we aim to effectively study the structural non-homogeneities within the arrays of zinc oxide nanowires (ZnO-NWs). The assessment of the lateral gradient of the nanowires' characteristics is presented including their height and surface density. To this end, spectroscopic ellipsometry and the rather recently reported technique of spectral domain attenuated reflectometry are used as two fast, simple and non-invasive characterization methods with further capabilities of scanning over the sample surface. Simple models are proposed by considering ZnO-NWs as the equivalent of thin stratified layers based on the effective medium approach. The methodology not only reveals the presence of gradients, but also enables quantitative analysis for all the samples grown using the hydrothermal method with different growth times ranging from 0.5 h up to 4 h. The gradients are confirmed using scanning electron microscopy (SEM) observations taken as a reference. The results also suggest that the sample orientation during the growth influences the NW growth besides the other parameters already known to affect the growth mechanisms.

On-chip parallel Fourier transform spectrometer for broadband selective infrared spectral sensing.

Optical spectrometers enable contactless chemical analysis. However, decreasing both their size and cost appears to be a prerequisite to their widespread deployment. Chip-scale implementation of optical spectrometers still requires tackling two main challenges. First, operation over a broad spectral range extending to the infrared is required to enable covering the molecular absorption spectrum of a broad variety of materials. This is addressed in our work with an Micro-Electro Mechanical Systems (MEMS)-based Fourier transform infrared spectrometer with an embedded movable micro-mirror on a silicon chip. Second, fine spectral resolution Δλ is also required to facilitate screening over several chemicals. A fundamental limit states that Δλ is inversely proportional to the mirror motion range, which cannot exceed the chip size. To boost the spectral resolution beyond this limit, we propose the concept of parallel (or multi-core) FTIR, where multiple interferometers provide complementary optical paths using the same actuator and within the same chip. The concept scalability is validated with 4 interferometers, leading to approximately 3 times better spectral resolution. After the atmospheric contents of a greenhouse gas are monitored, the methane absorption bands are successfully measured and discriminated using the presented device.

Micro-Electro-Mechanical System Fourier Transform Infrared (MEMS FT-IR) Spectrometer Under Modulated-Pulsed Light Source Excitation.

Miniaturized Fourier transform infrared (FT-IR) spectrometers suffer from limited optical throughput due to their tiny aperture size. Therefore, coherent wideband sources with high brightness can provide an advantage over the wideband thermal radiation sources. However, the former ones are available based on pulsed operation. In this work, we present and study a miniaturized FT-IR spectrometer with pulsed light sources including chopped thermal source, semiconductor optical amplifier, Q-switched and femtosecond mode-locked laser sources. A system model for the FT-IR spectrometer system under a modulated input light source is presented. The model accounts for the relatively high scanning speed of the micro-electro-mechanical system (MEMS) interferometer. The signal-to-noise ratio of the spectrometer, due to the light source modulation, is calculated at different values of modulation repetition rate ranging from 20 Hz to 2 MHz, and duty cycle values ranging from 1% to 50%. An analytical expression for the worst-case repetition rate for the spectrometer system is derived. The model results are verified by experimental measurements showing good agreement with the theoretical expectations. Spectroscopic measurements for CO2 gas with pressure ranging from 300 mbar to 700 mbar are also performed using a high-repetition rate source, and the measured spectra agree with the simulation results demonstrating the utility of the spectrometer.

Autoregressive superresolution microelectromechanical systems Fourier transform spectrometer.

In this work, the application of the superresolution autoregressive (AR) model to enhance the resolution of the microelectromechanical systems (MEMS) Fourier transform infrared spectrometer (FTIR) spectrometer is studied theoretically and experimentally. The effect of the number of spectral lines, the spacing between the lines, the resolution of the MEMS FTIR spectrometer and the signal-to-noise ratio (SNR) on the prediction accuracy is addressed for different targeted prediction resolutions. The effect of the SNR on applying the AR model is studied. Then, the AR model is applied to experimental data obtained using the MEMS FTIR for the different cases of single spectral line, xenon lamp lines and gas cells containing different gas mixtures. It is found that enhancement up to 4× can obtained in the case of the single line, while an enhancement of about 2-2.5× can be obtained in the case of multilines without having false spectral lines.

Nanowire Length, Density, and Crystalline Quality Retrieved from a Single Optical Spectrum.

We propose spectral domain attenuated reflectometry (SDAR) for fast characterization of nanomaterial growth. The method is demonstrated here for zinc oxide (ZnO) nanowires (NWs) which are grown vertically in random forest fashion showing that it is not limited to well-ordered NWs. We show how SDAR can provide, on the basis of a single measured spectrum, simultaneous information on nanowire length, nanowire density (through nanowire/air filling ratio), and crystalline quality (through band gap). The robustness of the proposed method is assessed first through comparison with information obtained from SEM and XRD taken as reference. In SDAR, the process for fast extraction of NW thickness and filling ratio values  makes use of the interference pattern contrast and the spectral periodicity in the reflection response which involve a best fit of the measured spectra with simple theoretical modeling based on the effective medium approach, achieved with a mean square error down to 0.1%. The results also suggest the existence of either 2 or 3 layers of different effective refractive index, hence providing insight on possible growth mechanisms.

On-Channel Integrated Optofluidic Pressure Sensor with Optically Boosted Sensitivity.

A novel optofluidic sensor that measures the local pressure of the fluid inside a microfluidic channel is presented. It can be integrated directly on-channel and requires no additional layers in fabrication. The detection can be accomplished at a single wavelength; and thereby, only a single laser diode and a single photodetector are required. This renders the sensor to be compact, cheap and easy to fabricate. Basically, the sensor consisted of a Fabry⁻Pérot microresonator enclosing the fluidic channel. A novel structure of the Fabry⁻Pérot was employed to achieve high-quality factor, that was essential to facilitate the single wavelength detection. The enhanced performance was attributed to the curved mirrors and cylindrical lenses used to avoid light diffraction loss. The presented sensor was fabricated and tested with deionized water liquid and shown to exhibit a sensitivity up to 12.46 dBm/bar, and a detection limit of 8.2 mbar. Numerical simulations are also presented to evaluate the mechanical⁻fluidic performance of the device.

High-Q Fabry⁻Pérot Micro-Cavities for High-Sensitivity Volume Refractometry.

This work reports a novel structure for a Fabry⁻Pérot micro cavity that combines the highest reported quality factor for an on-chip Fabry⁻Pérot resonator that exceeds 9800, and a very high sensitivity for an on-chip volume refractometer based on a Fabry⁻Pérot cavity that is about 1000 nm/refractive index unit (RIU). The structure consists of two cylindrical Bragg micromirrors that achieve confinement of the Gaussian beam in the plan parallel to the chip substrate, while for the perpendicular plan, external fiber rod lenses (FRLs) are placed in the optical path of the input and the output of the cavity. This novel structure overcomes number of the drawbacks presented in previous designs. The analyte is passed between the mirrors, enabling its detection from the resonance peak wavelengths of the transmission spectra. Mixtures of ethanol and deionized (DI)-water with different ratios are used as analytes with different refractive indices to exploit the device as a micro-opto-fluidic refractometer. The design criteria are detailed and the modeling is based on Gaussian-optics equations, which depicts a scenario closer to reality than the usually used ray-optics modeling.

Transformation algorithm and analysis of the Fourier transform spectrometer based on cascaded Fabry-Perot interferometers.

The Fourier transform spectrometer based on cascaded Fabry-Perot interferometers is analyzed, where one of the interferometers has a fixed length, while the other is scanning. We propose a method to reconstruct the spectrum correctly based on solving the integral equation of the overall response of the cascaded interferometers. The method is tested for different design parameters and noise conditions. Low reconstruction error below -80 dB is found to be achievable.