Mid-infrared Spectral Range Research Articles

Progress and Perspectives of Mid-Infrared Photoacoustic Spectroscopy for Non-Invasive Glucose Detection.

The prevalence of diabetes is rapidly increasing worldwide and can lead to a range of severe health complications that have the potential to be life-threatening. Patients need to monitor and control blood glucose levels as it has no cure. The development of non-invasive techniques for the measurement of blood glucose based on photoacoustic spectroscopy (PAS) has advanced tremendously in the last couple of years. Among them, PAS in the mid-infrared (MIR) region shows great promise as it shows the distinct fingerprint region for glucose. However, two problems are generally encountered when it is applied to monitor real samples for in vivo measurements in this MIR spectral range: (i) low penetration depth of MIR light into the human skin, and (ii) the effect of other interfering components in blood, which affects the selectivity of the detection system. This review paper systematically describes the basics of PAS in the MIR region, along with recent developments, technical challenges, and data analysis strategies, and proposes improvements for the detection sensitivity of glucose concentration in human bodies. It also highlights the recent trends of incorporating machine learning (ML) to enhance the detection sensitivity of the overall system. With further optimization of the experimental setup and incorporation of ML, this PAS in the MIR spectral region could be a viable solution for the non-invasive measurement of blood glucose in the near future.

Hierarchical Surface Structures and Large-Area Nanoscale Gratings in As2S3 and As2Se3 Films Irradiated with Femtosecond Laser Pulses.

Chalcogenide vitreous semiconductors (ChVSs) find application in rewritable optical memory storage and optically switchable infrared photonic devices due to the possibility of fast and reversible phase transitions, as well as high refractive index and transmission in the near- and mid-infrared spectral range. Formed on such materials, laser-induced periodic surface structures (LIPSSs), open wide prospects for increasing information storage capacity and create polarization-sensitive optical elements of infrared photonics. In the present work, a possibility to produce LIPSSs under femtosecond laser irradiation (pulse duration 300 fs, wavelength 515 nm, repetition rate up to 2 kHz, pulse energy ranged 0.03 to 0.5 μJ) is demonstrated on a large (up to 5 × 5 mm2) area of arsenic sulfide (As2S3) and arsenic selenide (As2Se3) ChVS films. Scanning electron and atomic force microscopy revealed that LIPSSs with various periods (170-490 nm) and orientations can coexist within the same irradiated region as a hierarchical structure, resulting from the interference of various plasmon polariton modes generated under intense photoexcitation of nonequilibrium carriers within the film. The depth of the structures varied from 30 to 100 nm. The periods and orientations of the formed LIPSSs were numerically simulated using the Sipe-Drude approach. A good agreement of the calculations with the experimental data was achieved.

Intra-pulse difference frequency generation in ZnGeP2 for high-frequency terahertz radiation generation

The highly-nonlinear chalcopyrite crystal family has experienced remarkable success as source crystals in the mid-infrared spectral range, such that these crystals are primary candidates for producing high terahertz frequency (i.e., gtrsim 10 THz) electric fields. A phase-resolved terahertz electric field pulse is produced via intra-pulse difference frequency generation in a chalcopyrite (110) ZnGeP2 crystal, with phase-matching being satisfied by the excitation electric field pulse having polarizations along both the ordinary and extraordinary crystal axes. While maximum spectral power is observed at the frequency of 24.5 THz (in agreement with intra-pulse phase-matching calculations), generation nonetheless occurs across the wide spectral range of 23–30 THz. To our knowledge, this is the first time a chalcopyrite ZnGeP2 crystal has been used for the generation of phase-resolved high-frequency terahertz electric fields.

Mid- and far-infrared spectroscopy of nucleobases: molar extinction coefficients, integrated molar absorptivity, and temperature dependence of the main bands

ABSTRACT The nucleobases, namely the purines adenine and guanine and the pyrimidines cytosine, thymine, and uracil, are the key monomers of the information polymers DNA and RNA. All the nucleobases were recently detected in the analysis of certain meteorites known as carbonaceous chondrites. The concentration of the nucleobases found in meteorites is smaller than the concentration of amino acids. However, the nucleobases were successfully synthesized abiotically by ultraviolet irradiation of interstellar ice analogues at 10 K. Consequently, it is possible that the purines and pyrimidines may be present in the interstellar medium or in other space environments and may be detectable by the new orbiting telescopes that indeed are able to cover not only the mid-infrared spectral range but also the far-infrared. This work supplies the reference spectra of the five nucleobases used by the terrestrial biochemistry in the mid-infrared and in the far-infrared with the purpose to facilitate the search and identification of these astrobiological and astrochemical relevant molecules in space. The mid-infrared spectra of all nucleobases were recorded at three different temperatures from −180 °C to nearly ambient temperature and at +250 °C. Furthermore, the molar extinction coefficients (ε) of all mid- and far-infrared bands were determined, as well as the integrated molar absorptivities (ψ). With the reported infrared spectra together with the ε and ψ values, it will be possible to identify qualitatively the nucleobases and estimate their relative abundance in space.

High-harmonic generation from a subwavelength dielectric resonator.

Higher-order optical harmonics entered the realm of nanostructured solids being observed recently in optical gratings and metasurfaces with a subwavelength thickness. Structuring materials at the subwavelength scale allows us toresonantly enhance the efficiency of nonlinear processes and reduce the size of high-harmonic sources. We report the observation of up to a seventh harmonic generated from a single subwavelength resonator made of AlGaAs material. This process is enabled by careful engineering of the resonator geometry for supporting an optical mode associated with a quasi-bound state in the continuum in the mid-infrared spectral range at around λ=3.7 μm pump wavelength. The resonator volume measures ~0.1 λ3. The resonant modes are excited with an azimuthally polarized tightly focused beam. We evaluate the contributions of perturbative and nonperturbative nonlinearities to the harmonic generation process. Our work proves the possibility to miniaturize solid-state sources of high harmonics to the subwavelength volumes.

Diffraction-limited hyperspectral mid-infrared micro-ellipsometry.

The recent introduction of quantum cascade lasers (QCL) in infrared spectroscopic ellipsometry led to decisive improvements in measurement times and signal-to-noise ratios of this powerful analytical method. In this contribution, we present another significant enhancement leading to the first, to the best of our knowledge, diffraction-limited micro-ellisometry setup in the mid-infrared spectral range with a spatial resolution better than 13.3 µm. The fast spectral tunability of the QCL combined with phase-modulated polarization enabled simultaneous acquisition of broadband (900 cm-1-1204 cm-1) high-resolution (1 cm-1) hyperspectral Ψ, Δ-cubes in a scanning approach in reasonable time scales. The spatial resolution of the QCL micro-ellipsometer was experimentally characterized by the knife-edge method and measurements of a resolution test target. Furthermore, the hyperspectral ellipsometric investigation of a polymer multilayer cross section and the portrait window of a 200-euro bank note demonstrate the capabilities of diffraction-limited QCL micro-ellipsometry.

Bending Loss Analysis of Chalcogenide Glass Channel Waveguides for Mid-Infrared Astrophotonic Devices

In this study, the bending losses of chalcogenide glass channel optical waveguides consisting of an As2Se3 core and an As2S3 lower cladding layer were numerically evaluated across the astronomical N-band, which is the mid-infrared spectral range between the 8 µm and 12 µm wavelengths. The results reveal the design rules for bent waveguides in mid-infrared astrophotonic devices.

Broadband Mie scattering effects by structural features of setae from the Saharan silver ant Cataglyphis bombycina

The Saharan desert ant Cataglyphis bombycina is densely covered with shiny silver setae (hair-like structures). Their appearance was explained by geometric optics and total internal reflection [Plos One 11, e0152325 (2016)POLNCL1932-620310.1371/journal.pone.0152325]. The setae also increase the emissivity of the ant, as they form an effective medium [Science 349, 298 (2015)SCIEAS0036-807510.1126/science.aab3564]. This work provides additional data on microstructural details of the setae that are used to simulate the scattering of an individual seta to explain their influence on the optical properties. This is achieved by characterization of their structure using light microscopy and scanning/transmission electron microscopy. How the microstructural features influence scattering is investigated wave-optically within the limits of finite-difference time-domain simulations from the ultraviolet to the mid-infrared spectral range to elucidate the optical effects beyond ray optics and effective medium theory. The results show that Mie scattering plays an important role in protecting the ant from solar radiation and could be relevant for its thermal tolerance.

Large mode-area all-solid anti-resonant fiber based on chalcogenide glass for mid-infrared transmission.

A large mode-area chalcogenide all-solid anti-resonant fiber has been designed and successfully prepared for the first time. The numerical results show that the high-order mode extinction ratio of the designed fiber can reach 6000, and the maximum mode-area is 1500 um2. The fiber possesses a calculated low bending loss of less than 10-2 dB/m as the bending radius is larger than 15 cm. In addition, there is a low normal dispersion of -3 ps/nm/km at 5 μm, which is beneficial for the transmission of high power mid-infrared laser. Finally, a completely structured all-solid fiber was prepared by the precision drilling and two-stage rod-in-tube methods. The fabricated fibers transmit in the mid-infrared spectral range from 4.5 to 7.5 μm with the lowest loss of 7 dB/m @ 4.8 μm. Modeling suggests that the theoretical loss of the optimized structure is consistent with that of the prepared structure in the long wavelength band.

Highly Responsive Mid-Infrared Metamaterial Enhanced Heterostructure Photodetector Formed out of Sintered PbSe/PbS Colloidal Quantum Dots.

Efficient and simple-to-fabricate light detectors in the mid infrared (MIR) spectral range are of great importance for various applications in existing and emerging technologies. Here, we demonstrate compact and efficient photodetectors operating at room temperature in a wavelength range of 2710-4250 nm with responsivities as high as 375 and 4 A/W. Key to the high performance is the combination of a sintered colloidal quantum dot (CQD) lead selenide (PbSe) and lead sulfide (PbS) heterojunction photoconductor with a metallic metasurface perfect absorber. The combination of this photoconductor stack with the metallic metasurface perfect absorber provides an overall ∼20-fold increase of the responsivity compared against reference sintered PbSe photoconductors. More precisely, the introduction of a PbSe/PbS heterojunction increases the responsivity by a factor of ∼2 and the metallic metasurface enhances the responsivity by an order of magnitude. The metasurface not only enhances the light-matter interaction but also acts as an electrode to the detector. Furthermore, fabrication of our devices relies on simple and inexpensive methods. This is in contrast to most of the currently available (state-of-the-art) MIR photodetectors that rely on rather expensive as well as nontrivial fabrication technologies that often require cooling for efficient operation.

Designing broadband dispersive mirrors in the mid-infrared spectral range: a theoretical study.

The study reports practically important and interesting results on designing dispersive mirrors (DMs) operating in the mid-infrared spectral range from 3 to 18µm. The admissible domains of the most important design specifications, the mirror bandwidth and group delay variation, were constructed. Estimations of the required total coating thickness, thickness of the thickest layer, and expected number of layers are obtained. The results are confirmed by an analysis of several hundreds of DM design solutions.

Relaxing Graphene Plasmon Excitation Constraints Through the Use of an Epsilon-Near-Zero Substrate

Graphene plasmons have attracted significant attention due to their tunability, potentially long propagation lengths and ultracompact wavelengths. However, the latter characteristic imposes challenges to light-plasmon coupling in practical applications, generally requiring sophisticated coupling setups, extremely high doping levels and/or graphene nanostructuring close to the resolution limit of current lithography techniques. Here, we propose and theoretically demonstrate a method for alleviating such a technological strain through the use of a practical substrate whose low and negative dielectric function naturally enlarges the graphene polariton wavelength to more manageable levels. We consider silicon carbide (SiC), as it exhibits a dielectric function whose real part is between \(-1\) and 0, while its imaginary part remains lower than 0.05, in the 951 to 970 cm\(^{-1}\) mid-infrared spectral range. Our calculations show hybridization with the substrate’s phonon polariton, resulting in a polariton wavelength that is an order of magnitude longer than obtained with a silicon dioxide substrate, while the propagation length increases by the same amount.

Broadband saturable absorption of indium tin oxide nanocrystals toward mid-infrared regime.

We experimentally demonstrate the ultrabroadband optical nonlinearity of indium tin oxide nanocrystals (ITO NCs) in the mid-infrared regime. Especially, the ITO NCs show considerable saturation absorption behavior with large modulation depth covering the spectral range from 2-µm to 10-µm wavelength. We also demonstrate the application of the optical nonlinearity to successfully modulate the erbium-doped fluoride fiber laser to deliver a nanosecond pulse with a signal-to-noise ratio over 43 dB at 2.8-µm wavelength. The results provide a promising platform for the development of ITO-based broadband and robust optoelectronic devices toward the deep mid-infrared spectral range.

VO2 particle-based intelligent metasurface with perfect infrared emission for the spacecraft thermal control.

Thermochromism film can automatically adjust its emittance without additional energy consumption, which shows great prospect in the application of spacecraft thermal control. However, it is still challenging to achieve a large infrared emittance at a high temperature and emittance tunability of the thermochromism film. In this work, we propose a V O 2 particle-based intelligent metasurface for spacecraft thermal control, which consists of a square lattice array of hollow spheroidal V O 2 particles on Au substrate. The metasurface with a V O 2 particle having a large aspect ratio (∼10) displays perfect emission throughout the entire mid-infrared spectral range. The emittance tunability can exceed 0.63 with total normal emittance of 0.85. The underlying mechanisms involved in the metasurface are attributed to particle-dependent scattering, by which the infrared emittance is dramatically enhanced for the metallic state and restricted for the dielectric state. In addition, the infrared emittance at a high temperature and emittance tunability of the metasurface remain large for incident angles up to 60°. To the best of our knowledge, this work proposes the first thermochromism film structure with perfect infrared emission, which could accelerate the development and practical application of the thermochromic film in the field of spacecraft.

Thermally stable high numerical aperture integrated waveguides and couplers for the 3 μm wavelength range

The femtosecond laser direct write technique was used to fabricate mid-infrared compatible waveguide couplers into Suprasil 3001, a fused silica glass with an OH content of as low as ≤1 ppm. Smooth positive step-index change multi-scan waveguides were produced with a high index contrast of 1 × 10−2, measured directly using quadriwave lateral shearing interferometry. Waveguides were annealed at 400 °C for 15 h and found to be highly stable, with only <5% reduction in positive index change. Brillouin microscopy and cathodoluminescence are introduced as novel tools that complement Raman mapping and electron microscopy for the investigation of the laser-induced structural changes within the glass matrix, and it was found that although a uniform step index profile is observed across the entire guiding region, different physical mechanisms underpin the index change in the upper and lower sections of the waveguide cross-section, respectively. Waveguides were optimized for mode-matching with optical fibers for the 3.2 μm wavelength range, and evanescent four-port directional couplers with coupling ratios ranging from 5:95 to 50:50 were designed and fabricated. This demonstration opens the door to the development of fully integrated and temperature-stable hybrid chip/fiber systems for the important mid-infrared spectral range.

Fused optical fiber combiner based on indium fluoride glass: perspectives for mid-IR applications.

For the first time, to the best of our knowledge, the design and characterization of a 3 × 1 fused fiber combiner based on multimode step-index fluoroindate optical fibers (InF3) has been performed. Several efforts to develop a well-consolidated normalization procedure and a fabrication protocol have been required due to the low melting temperature and the mechanical properties of fluoroindates. Fabrication results demonstrate repeatability and absence of crystallization. Therefore, the described fabrication process paves the way for manufacturing fluoroindate devices. The electromagnetic design of the combiner is carried out through modal investigation and beam propagation method by computing the transmission efficiency. The experimental results agree with the simulation and demonstrate the device feasibility to operate in the mid-infrared spectral range.

The detection of SF6 decomposition components SO2F2, SOF2 using mid-infrared TDLAS at 6.635 µm and 7.462 µm

SO2F2 and SOF2 are the main SF6 decomposition products, and the accurate detection of trace SO2F2 and SOF2 is of great significance to evaluate the internal insulation of the electrical equipment. In general, gas molecules have strong absorption coefficient in the mid-infrared spectral range, which can achieve very low detection limit and has great advantages in the detection of trace gases. In this paper, the quantum cascade lasers at 6.635 µm and 7.462 µm in the mid-infrared band are used as the light source of tunable diode laser absorption spectroscopy (TDLAS) to detect trace SO2F2 and SOF2. The results show that the second harmonic signal peak values of SO2F2 and SOF2 have a good linear relationship with the gas concentration. The linear fits of SO2F2 and SOF2 are excellent at 0.99374 and 0.99785 respectively. The experimental platform has good stability, and the maximum errors are 0.00109 V, 0.00208 V, and 0.00125 V. Allan analysis shows that the detection limit of SO2F2 is 0.1628 μL/L when the integration time is 7.44 s. The detection limit of SOF2 is 0.0167 μL/L at 2.8 s. The research results can provide technical reference and support for the effective detection of SF6 decomposition components.

Label-free bacteria identification for clinical applications.

We have developed a system for bacteria identification based on absorption spectroscopy in the mid-infrared spectral range. The data collected are analyzed with a deep learning algorithm. It is based on a neural-network model which takes one-dimensional signal vectors and outputs a probability score of identification of a bacterium type by extracting micro and macro scale features, using convolutions and nonlinear operations. The results are achieved in real time and do not require any offline postprocessing. The study was done on 12 of the most common bacteria usually seen in clinical microbiology laboratories. The system sensitivity is 0.94 ± 0.04, with a specificity of 0.95 ± 0.02. The system can be extended to additional bacterium types and variants with no change to its hardware or software, but only updating the model's parameters. The system's accuracy, size, ease of operation and low cost make it suitable for use in any type of clinical setting.

Mid-infrared all-optical wavelength converter based on highly nonlinear MXene-decorated microfiber

We propose an all-optical wavelength converter for the mid-infrared spectral range with enhanced conversion efficiency. A highly nonlinear MXene-decorated microfiber is fabricated by the optical deposition method as the conversion medium, and the fiber exhibits a remarkable nonlinear optical response. We combine the benefits of the two-dimensional MXene materials and tapered microfiber to promote conversion efficiency. Homebuilt holmium-doped fiber lasers emitting at 2.05 μm wavelength are used as pump and signal sources. The experimental conversion efficiency observed by the optical spectrum analyzer is measured at –27.22 dB. This optical device allows an arbitrary tuning range of 17 nm. The fluctuations of the conversion efficiency remain within 1 dB during 2 h. The results of this study may contribute to the realization of optical converter application in the all-optical network at 2 μm wavelength.

VO2-based superposed Fabry-Perot multilayer film with a highly enhanced infrared emittance and emittance tunability for spacecraft thermal control.

Thermal control coating for spacecraft based on thermochromic film attracts increasing interest due to their ability of self-adaptive emittance switch and less resource consuming compared with traditional thermal control coatings. However, practical applications of thermochromic film for spacecraft are constrained by the low infrared emittance at a high temperature and narrow emittance tunability. In this work, a thermochromic film with simple structure, nearly perfect infrared emission and large emittance tunability is proposed for the application of spacecraft thermal control. The thermochromic film is a VO2-based superposed Fabry-Perot (FP) multilayer film, which is constructed by encapsulating three thin VO2 layers in four lossless BaF2 spacer on the Al substrate. The infrared emittance and emittance tunability of the superposed FP film is dramatically enhanced by the three superposed VO2-BaF2-Al FP resonances at wavelengths of 9, 15 and 20 µm, respectively. For VO2 layers under metallic state, the spectral normal emittance of the superposed FP film is close to unity in the entire mid-infrared spectral range, while for VO2 layers under dielectric state, the film is highly reflective. For the typical growth techniques of the VO2 layers considered here, the emittance tunability of the superposed FP film can exceed 0.70 with total normal emittance larger than 0.91 at high temperature, simultaneously. The largest total normal emittance of the superposed FP film can reach 0.95 with emittance tunability of 0.78. In addition, the infrared emission and emittance tunability performances of the superposed FP film remain excellent for incident angles up to 60°. This work proposes a simple structure with highly enhanced infrared emittance and emittance tunability that outperforms the existing thermochromic films, which could accelerate the application of thermochromic films in the field of spacecraft thermal control.