Mid-infrared Dual-comb Spectroscopy Research Articles

Mid-infrared dual-comb spectroscopy with quantum cascade lasers

Since its invention in 1994, the quantum cascade laser (QCL) has emerged as a versatile light source of wavelength 4–12 µm, covering most of the mid- and long-wavelength infrared spectral ranges. Its application range has widened even further since frequency comb operation and its use as a light source for dual-comb spectroscopy (DCS) was demonstrated. In this tutorial, we introduce the unique properties of QCL frequency combs, such as high optical power, multi-GHz repetition rate, and narrow optical linewidths. Implemented in a dual-comb spectroscopy setup, this allows for broadband, low-noise measurements of strongly absorbing samples with sub-microsecond time resolution, and spectral resolution better than 10−3 cm−1/30 MHz. The advantages of QCL DCS will be discussed in the context of its broad range of applications. The high optical power (both total and per comb tooth) is leveraged for measurements in aqueous solution or at large stand-off distances. Microsecond temporal resolution measurements address the demand for probing rapid protein dynamics and combustion diagnostics. MHz-level spectral resolution, in turn, facilitates accurate line parameter studies in low pressure and cold molecular gases. Future development directions of the technology are discussed, including sub-microsecond response DCS, instrument miniaturization, or its expansion toward THz frequencies. Overall, the tutorial aims at giving a broad introduction to QCL DCS and its applications.

High-SNR mid-infrared dual-comb spectroscopy using active phase control cooperating with CWs-dependent phase correction.

Mid-infrared (MIR) dual-comb spectroscopy (DCS) is a highly effective method for molecular metrology of rovibrational transition spectra in a quick accurate manner. However, due to limited comb frequency instability, manipulating coherence between two frequency combs to accomplish high-quality spectral analysis in the MIR region is a huge challenge. Here, we developed a comb-teeth resolved MIR DCS based on active phase control cooperating with a CWs-dependent (CWD) interferogram timing correction. Firstly, four meticulously engineered actuators were individually integrated into two near-infrared (NIR) seed combs to facilitate active coherence maintenance. Subsequently, two PPLN waveguides were adopted to achieve parallel difference frequency generations (DFG), directly achieving a coherent MIR dual-comb spectrometer. To improve coherence and signal-to-noise ratio (SNR), a CWD resampled interferogram timing correction was used to optimize the merit of DCS from 7.5 × 105 to 2.5 × 106. Meanwhile, we carried out the measurement of MIR DCS on the methane hot-band absorption spectra (v3 band), which exhibited a good agreement with HITRAN by a standard deviation on recording residual of 0.76%. These experimental results confirm that this MIR DCS with CWD interferogram timing correction has significant potential to characterize the rovibrational transitions of MIR molecules.

Mid-infrared dual-comb spectroscopy for rapid temperature distribution characterization.

Due to the influence of chemical reactions, phase change, and other phenomena, the combustion system is a complicated high-temperature environment. Therefore, the spatio-temporally resolved monitoring of the temperature field is crucial for gaining a comprehensive understanding of the intricate combustion environment. In this study, we proposed a fast and high-precision temperature measurement technique based on mid-infrared (MIR) dual-comb spectroscopy with a high spectral resolution and fast refresh rate. Based on this technique, the spatio-temporally resolved measurement of a non-uniform temperature field was achieved along the laser path. To verify the capability of DCS for temperature measurement, the bandhead ro-vibrational lines of the CO2 molecule were acquired, and the 1-σ uncertainty of the retrieved temperature was 3.2°C at 800°C within 100 ms. The results demonstrate the potential of our fast and high-precision laser diagnostic technique which can be further applied to combustion kinetics.

Measurement of 24-h continuous human CH4 release in a whole room indirect calorimeter.

We describe the technology and validation of a new whole room indirect calorimeter (WRIC) methodology to quantify volume of methane (VCH4) released from the human body over 24 h concurrently with the assessment of energy expenditure and substrate utilization. The new system extends the assessment of energy metabolism by adding CH4, a downstream product of microbiome fermentation that could contribute to energy balance. Our new system consists of an established WRIC combined with the addition of off-axis integrated-cavity output spectroscopy (OA-ICOS) to measure CH4 concentration ([CH4]). Development, validation, and reliability of the system included environmental experiments to measure the stability of the atmospheric [CH4], infusing CH4 into the WRIC and human cross-validation studies comparing [CH4] quantified by OA-ICOS and mid-infrared dual-comb spectroscopy (MIR DCS).Our infusion data indicated that the system measured 24-h [CH4] and VCH4 with high sensitivity, reliability, and validity. Cross-validation studies showed good agreement between OA-ICOS and MIR DCS technologies (r = 0.979, P < 0.0001). Human data revealed 24-h VCH4 was highly variable between subjects and within/between days. Finally, our method to quantify VCH4 released by breath or colon suggested that over 50% of the CH4 was eliminated through the breath. The method allows, for the first time, measurement of 24-h VCH4 (in kcal) and therefore the measurement of the proportion of human energy intake fermented to CH4 by the gut microbiome and released via breath or from the intestine; also, it allows us to track the effects of dietary, probiotic, bacterial, and fecal microbiota transplantation on VCH4.NEW & NOTEWORTHY This is the first time that continuous assessment of CH4 is reported in parallel with measurements of O2 consumption and CO2 production inside a whole room indirect calorimeter in humans and over 24 h. We provide a detailed description of the whole system and its parts. We carried out studies of reliability and validity of the whole system and its parts. CH4 is released in humans during daily activities.

Dual-comb optical parametric oscillator in the mid-infrared based on a single free-running cavity.

We demonstrate a free-running single-cavity dual-comb optical parametric oscillator (OPO) pumped by a single-cavity dual-comb solid-state laser. The OPO ring cavity contains a single periodically-poled MgO-doped LiNbO3 (PPLN) crystal. Each idler beam has more than 245-mW average power at 3550 nm and 3579 nm center wavelengths (bandwidth 130 nm). The signal beams are simultaneously outcoupled with more than 220 mW per beam at 1499 nm and 1496 nm center wavelength. The nominal repetition rate is 80 MHz, while the repetition rate difference is tunable and set to 34 Hz. To evaluate the feasibility of using this type of source for dual-comb applications, we characterize the noise and coherence properties of the OPO signal beams. We find ultra-low relative intensity noise (RIN) below -158 dBc/Hz at offset frequencies above 1 MHz. A heterodyne beat note measurement with a continuous wave (cw) laser is performed to determine the linewidth of a radio-frequency (RF) comb line. We find a full-width half-maximum (FWHM) linewidth of around 400 Hz. Moreover, the interferometric measurement between the two signal beams reveals a surprising property: the center of the corresponding RF spectrum is always near zero frequency, even when tuning the pump repetition rate difference or the OPO cavity length. We explain this effect theoretically and discuss its implications for generating stable low-noise idler combs suitable for high-sensitivity mid-infrared dual-comb spectroscopy (DCS).

Two-component gas sensing with MIR dual comb spectroscopy

Abstract A dual comb spectrometer is used as gas sensor for the parallel detection of nitrous oxide (N2O) and carbon monoxide (CO). These gases have overlapping absorption features in the mid-infrared (MIR) at a wavelength of 4.6 µm. With a spectra acquisition rate of 10 Hz, concentrations of 50 ppm N2O and 30 ppm CO are monitored with a relative precision of 6 × 10 − 3 6\times {10^{-3}} and 3 × 10 − 3 3\times {10^{-3}} respectively. The limit of detections are 91 ppb for N2O and 50 ppb for CO for an integration time of 25 s. The system exhibits a linear sensitivity from 2 ppm to 100 ppm with coefficients of determination of 0.99998 for N2O and 0.99996 for CO.

Broadband mid-infrared molecular spectroscopy based on passive coherent optical–optical modulated frequency combs

Mid-infrared dual-comb spectroscopy is of great interest owing to the strong spectroscopic features of trace gases, biological molecules, and solid matter with higher resolution, accuracy, and acquisition speed. However, the prerequisite of achieving high coherence of optical sources with the use of bulk sophisticated control systems prevents their widespread use in field applications. Here we generate a highly mutually coherent dual mid-infrared comb spectrometer based on the optical–optical modulation of a continuous-wave (CW) interband or quantum cascade laser. Mutual coherence was passively achieved without post-data processes or active carrier envelope phase-locking processes. The center wavelength of the generated mid-infrared frequency combs can be flexibly tuned by adjusting the wavelength of the CW seeds. The parallel detection of multiple molecular species, including C 2 H 2 , CH 4 , H 2 CO , H 2 S , COS, and H 2 O , was achieved. This technique provides a stable and robust dual-comb spectrometer that will find nonlaboratory applications including open-path atmospheric gas sensing, industrial process monitoring, and combustion.

Mid-infrared dual frequency comb spectroscopy for combustion analysis from 2.8 to 5 µm

We demonstrate the application of mode-locked mid-infrared dual frequency comb spectroscopy for combustion analysis. With two settings of the same dual-comb system, the measurement spans 1500 cm−1 from 2.8 to 5 µm with 0.0067 cm−1 (200 MHz) point spacing, or almost a quarter-million discrete comb modes. Using this broadband spectrometer, we quantify the pyrolysis and smoldering combustion of wood samples. Specifically, we measure 20-second time-resolved mole fractions of CH4, H2O, two isotopologues of CO2 (12C16O2, 13C16O2), two isotopologues of CO (12C16O, 13C16O), ethane, formaldehyde, methanol, formic acid, as well as gas temperature directly above radiatively heated wood samples. The combination of the fine spectral resolution and the broad bandwidth of the dual-comb spectrometer allows for precise separation of absorption signatures of individual molecules from the congested spectra.

Nanophotonic supercontinuum-based mid-infrared dual-comb spectroscopy

High resolution and fast detection of molecular vibrational absorption is important for organic synthesis, pharmaceutical processes, and environmental monitoring, and is enabled by mid-infrared (mid-IR) laser frequency combs via dual-comb spectroscopy. Here, we demonstrate a novel and highly simplified approach to broadband mid-IR dual-comb spectroscopy via supercontinuum generation, achieved using unprecedented nanophotonic dispersion engineering that allows for ultra-broadband and flat-envelope mid-IR frequency combs. Our mid-IR dual-comb spectrometer has an instantaneous bandwidth covering the functional group region from 2800 – 3600 c m − 1 , comprising more than 100,000 comb lines, enabling parallel gas-phase detection with a high sensitivity, sub-Doppler spectral resolution, and a high speed. In addition to the traditional functional groups, their isotopologues are also resolved in this supercontinuum-based dual-comb spectroscopy. Our approach combines well established fiber laser combs, digital coherent data averaging, and integrated nonlinear photonics, each in itself a state-of-the-art technology, signaling the emergence of mid-IR dual-comb spectroscopy for use outside of the protected laboratory environment.

An interband cascade platform permits on-chip mid-infrared dual-comb spectroscopy

Replacing the standard mercury-cadmium-telluride photodiode with an interband cascade detector brought a fully-integrated, broadband spectrometer one step closer to reality.

Mid-infrared dual-comb spectroscopy with room-temperature bi-functional interband cascade lasers and detectors

Interband cascade (IC) laser structures offer attractive potential for operation at room temperature as both broadband coherent sources of mid-infrared light and fast photodetectors. This makes the realization of extremely compact spectrometers on a monolithic platform possible, and even dual-comb spectroscopy (DCS) configurations. IC comb devices are perfect candidates for this configuration, since they develop near-THz-wide optical frequency comb spectra from a millimeter-sized cavity, using a multi-stage structure that can also function as a very fast photodetector. In this work, we leverage IC photodetectors with a gigahertz bandwidth to demonstrate a self-contained, free-running, room-temperature DCS system in the mid-infrared. The DCS system used detection by the same bi-functional IC device structure to measure 1,1-difluoroethane over ∼600 GHz of optical coverage around 3.6 µm. These results show that the IC platform is suitable for full integration as a broadband, high-resolution on-chip spectrometer in a future chemical sensing system.

Time-resolved mid-infrared dual-comb spectroscopy

Dual-comb spectroscopy can provide broad spectral bandwidth and high spectral resolution in a short acquisition time, enabling time-resolved measurements. Specifically, spectroscopy in the mid-infrared wavelength range is of particular interest, since most of the molecules have their strongest rotational-vibrational transitions in this “fingerprint” region. Here we report time-resolved mid-infrared dual-comb spectroscopy, covering ~300 nm bandwidth around 3.3 μm with 6 GHz spectral resolution and 20 μs temporal resolution. As a demonstration, we study a CH4/He gas mixture in an electric discharge, while the discharge is modulated between dark and glow regimes. We simultaneously monitor the production of C2H6 and the vibrational excitation of CH4 molecules, observing the dynamics of both processes. This approach to broadband, high-resolution, and time-resolved mid-infrared spectroscopy provides a new tool for monitoring the kinetics of fast chemical reactions, with potential applications in various fields such as physical chemistry and plasma/combustion analysis.

Mid-infrared dual-comb spectroscopy with absolute frequency calibration using a passive optical reference.

We demonstrate an absolute-frequency-calibrated mid-infrared dual-comb spectrometer by using a reference absorption cell. The source is based on a singly-resonant OPO containing two MgO:PPLN crystals in a common ring cavity, synchronously pumped by two mode-locked Yb-fiber lasers. The repetition-rate of the two pumps are stabilized while their offset frequencies and the OPO cavity length are not actively controlled. The reference spectrum is used to correct the frequency fluctuations in the sample spectrum providing a high-quality averaged spectrum with spectral resolution of 6 GHz and calibration precision of 120 MHz, without adding any complexity to the experimental setup or signal processing.

Mid-infrared dual-comb spectroscopy with interband cascade lasers.

Two semiconductor optical frequency combs, consuming less than 1W of electrical power, are used to demonstrate high-sensitivity mid-infrared dual-comb spectroscopy in the important 3-4μm spectral region. The devices are 4mm long by 4μm wide, and each emits 8mW of average optical power. The spectroscopic sensing performance is demonstrated by measurements of methane and hydrogen chloride with optical multi-pass cell sensitivity enhancement. The system provides a spectral coverage of 33 cm-1 (1THz), 0.32 cm-1 (9.7GHz) frequency sampling interval, and peak signal-to-noise ratio of ∼100 at 100μs integration time. The monolithic design, low drive power, and direct generation of mid-infrared radiation are highly attractive for portable broadband spectroscopic instrumentation in future terrestrial and space applications.

Mid-infrared dual-comb spectroscopy of volatile organic compounds across long open-air paths

Open-path measurements of atmospheric gas species in the air, including volatile organic compounds, are essential to quantify emissions from sources like oil and gas, forest fires, and industry. Here, we extend open-path dual-comb spectroscopy to probe the fundamental mid-infrared C-H stretch modes of volatile organic compounds over up to 1 km long open-air paths. The spectrometer’s high resolution and accuracy facilitates suppression of strong spectral clutter from atmospheric water and methane, allowing quantitative measurements of released acetone and isopropanol with a 1−σ sensitivity of 5.7 ppm·m and 2.4 ppm·m, respectively, and of ambient atmospheric ethane with a 1−σ sensitivity of 0.4 ppb, measured with 1 min time resolution over hours. These results underline the potential of dual-comb spectroscopy for quantifying emissions.

Background-free broadband absorption spectroscopy based on interferometric suppression with a sign-inverted waveform

Background-free methods have potentially superior detection sensitivity because of their ability to take advantage of the full laser power; they are therefore attractive to spectroscopists. We implement background-free Fourier transform spectroscopy based on coherent suppression of the background using an interferometer, whereby the central peak of the interferogram is suppressed without losing molecular absorption signatures. This results in the appearance of peaks rather than dips in the measured spectrum. The technique can be used with a variety of broadband spectroscopies and features advantages such as a reduction in the required detector dynamic range, the capability to perform quantitative measurements, and strongly enhanced sensitivity down to the quantum limit. We validated our method experimentally by performing mid-infrared dual-comb spectroscopy with a mixture of multiple molecular species over a broad wavelength range of 3–5 μm.

Real-time liquid-phase organic reaction monitoring with mid-infrared attenuated total reflectance dual frequency comb spectroscopy

We combine mid-infrared dual-comb spectroscopy with attenuated total reflectance measurements to provide in-situ monitoring of a chemical reaction. The mid-infrared dual-comb spectrometer measures quantitative absorption cross-sections of mesityl oxide and diacetone alcohol in the region of 3300–2700 cm−1 (3.0–3.7 μm). Based on these spectra, the system is then used to monitor the hydration of mesityl oxide to diacetone alcohol from which we extract reaction kinetics values. This work shows the potential of dual comb systems to measure and monitor reactions in the condensed phase.

Dual-comb spectroscopy using plasmon-enhanced-waveguide dispersion-compensated quantum cascade lasers

In this Letter, we report on sub-millisecond response time mid-infrared dual-comb spectroscopy using a balanced asymmetric (dispersive) dual-comb setup with a matched pair of plasmon-enhanced-waveguide dispersion-compensated quantum cascade lasers. The system performance is demonstrated by measuring spectra of Bromomethane (CH3Br) and Freon 134a (CH2FCF3) at approximately 7.8μm. A purely computational phase and timing-correction procedure is used to validate the coherence of the quantum cascade lasers frequency combs and to enable coherent averaging over the time scales investigated. The system achieves a noise-equivalent absorption better than 1×10-3 Hz-1/2, with a resolution of 9.8GHz (0.326 cm-1) and an optical bandwidth of 1THz (32 cm-1), with an average optical power of more than 1mW per spectral element.

Two-micron all-fibered dual-comb spectrometer based on electro-optic modulators and wavelength conversion

Mid-infrared dual-comb spectroscopy offers interesting applications since molecules have their strongest rotational–vibrational absorptions in this frequency domain. Besides, generating frequency combs with electro-optic modulators recently showed promising results toward dual-comb spectroscopy. Here, we report a conversion in the mid-infrared of two mutually coherent frequency combs generated with electro-optic modulators to perform dual-comb spectroscopy in this region. Using fourth-order modulation instability taking place in the normal dispersion regime of a highly nonlinear fiber and by seeding this phenomenon with a frequency agile and low-power laser around 1.3 μm, we develop a stable and wavelength tunable all-fibered dual-comb spectrometer operating in the 2 μm region. This allows us to investigate CO2 absorption spectra over 37 nm and to measure collisional broadening coefficients of a few rotational–vibrational lines.

Silicon-chip-based mid-infrared dual-comb spectroscopy

The development of a spectroscopy device on a chip that could realize real-time fingerprinting with label-free and high-throughput detection of trace molecules represents one of the big challenges in sensing. Dual-comb spectroscopy (DCS) in the mid-infrared is a powerful technique offering high acquisition rates and signal-to-noise ratios through use of only a single detector with no moving parts. Here, we present a nanophotonic silicon-on-insulator platform designed for mid-infrared (mid-IR) DCS. A single continuous-wave low-power pump source generates two mutually coherent mode-locked frequency combs spanning from 2.6 to 4.1 μm in two silicon microresonators. A proof-of-principle experiment of vibrational absorption DCS in the liquid phase is achieved acquiring spectra of acetone spanning from 2900 to 3100 nm at 127-GHz (4.2-cm−1) resolution. These results represent a significant step towards a broadband, mid-IR spectroscopy instrument on a chip for liquid/condensed matter phase studies.