Optical frequency-comb-based-high-resolution spectrometers offer enormous potential for spectroscopic applications. Although various implementations have been demonstrated, the lack of suitable mid-infrared comb sources has impeded explorations of molecular fingerprinting. Here we present for the first time a frequency-comb Fourier transform spectrometer operating in the 2100-to-3700-cm-1 spectral region that allows fast and simultaneous acquisitions of broadband absorption spectra with up to 0.0056 cm-1 resolution. We demonstrate part-per-billion detection limits in 30 seconds of integration time for various important molecules including methane, ethane, isoprene, and nitrous oxide. Our system enables precise concentration measurements even in gas mixtures that exhibit continuous absorption bands, and it allows detection of molecules at levels below the noise floor via simultaneous analysis of multiple spectral features. This system represents a near real-time, high-resolution, high-bandwidth mid-infrared spectrometer which is ready to replace traditional Fourier transform spectrometers for many applications in trace gas detection, atmospheric science, and medical diagnostics.
As a potent greenhouse gas and ozone depleting agent, nitrous oxide (N$_2$O) plays a critical role in the global climate. Effective mitigation relies on understanding global sources and sinks which can be supported through isotopic analysis. We present a cross-dispersed spectrometer, coupled with a mid-infrared frequency comb, capable of simultaneously monitoring all singly substituted, stable isotopic variants of N$_2$O. Rigorous evaluation of the instrument lineshape function and data treatment are discussed. Laboratory characterization of the spectrometer demonstrates sub-GHz spectral resol…
We demonstrate a high-accuracy dual-comb spectrometer centered at 3.4 μm. The amplitude and phase spectra of the P, Q, and partial R-branch of the methane ν3 band are measured at 25 MHz to 100 MHz point spacing with ~kHz resolution and a signal-to-noise ratio of up to 3500. A fit of the absorbance and phase spectra yield the center frequency of 132 rovibrational lines. The systematic uncertainty is estimated to be 300 kHz, which is 10-3 of the Doppler width and a tenfold improvement over Fourier transform spectroscopy. These data are the first high- accuracy molecular spectra obtained with a d…
Integrated mid-infrared micro-spectrometers have a great potential for applications in environmental monitoring and space exploration. Silicon-on-insulator (SOI) is a promising platform to tackle this integration challenge, due to its unique capability for large volume and low-cost production of ultra-compact photonic circuits. However, the use of SOI in the mid-infrared is restricted by the strong absorption of the buried oxide layer for wavelengths beyond 4 μm. Here, we overcome this limitation by utilizing metamaterial-cladded suspended silicon waveguides to implement a spatial heterodyne F…
We present and characterize a 2-D imaging spectrometer based on a virtually-imaged phased array (VIPA) disperser for rapid, high-resolution molecular detection using mid-infrared (MIR) frequency combs at 3.1 and 3.8 μm. We demonstrate detection of CH4 at 3.1 μm with >3750 resolution elements spanning >80 nm with ~600 MHz resolution in a <10 μs acquisition time. In addition to broadband detection, rapid, time-resolved single-image detection is demonstrated by capturing dynamic concentration changes of CH4 at a rate of ~375 frames per second. Changes in absorption above the noise floor of 5\time…
Mid-infrared (mid-IR) spectroscopy is a crucial workhorse for a plethora of analytical applications and is suitable for diverse materials, including gases, polymers or biological tissue. However, this technologically significant wavelength regime between 2.5-10$μ$m suffers from technical limitations primarily related to the large noise in mid-IR detectors and the complexity and cost of bright, broadband mid-IR light sources. Here, using highly non-degenerate, broadband photon pairs from bright spontaneous parametric down-conversion (SPDC) in a nonlinear interferometer, we circumvent these limi…
We demonstrate a robust and simple method for measurement, stabilization and tuning of the frequency of cw mid-infrared (MIR) lasers, in particular of quantum cascade lasers. The proof of principle is performed with a quantum cascade laser at 5.4 μm, which is upconverted to 1.2 μm by sum-frequency generation in orientation-patterned GaAs with the output of a standard high-power cw 1.5 μm fiber laser. Both the 1.2 μm and the 1.5 μm waves are measured by a standard Er:fiber frequency comb. Frequency measurement at the 100 kHz-level, stabilization to sub-10 kHz level, controlled frequency tuning …
East China Normal University（华东师范大学）；Chongqing Institute of East China Normal University（华东师范大学重庆研究院）；Shanxi University（山西大学）；Shanghai University（上海大学）
We present a 100 kHz broadband vibrational sum-frequency generation (VSFG) spectrometer operating in the 5.5-10.5 $μ$m (950-1750 cm$^{-1}$) wavelength range. The mid-infrared beam of the system is obtained from a collinear, type-I LiGaS$_{2}$ crystal based optical parametric amplifier seeded by a supercontinuum and pumped directly by 180 fs, ~32 $μ$J, 1.03 $μ$m pulses from an Yb:KGd(WO$_{4}$)$_{2}$ laser system. Up to 0.5 $μ$J mid-infrared pulses with durations below 100 fs were obtained after dispersion compensation utilizing bulk materials. We demonstrate the utility of the spectrometer by r…
Dual-frequency comb spectroscopy has emerged as a disruptive technique for measuring wide-spanning spectra with high resolution, yielding a particularly powerful technique for sensitive multi-component gas analysis. We present a spectrometer system based on dual electro-optical combs with subsequent conversion to the mid-infrared via tunable difference frequency generation, operating in the range from 3 to 4.7 $μ$m. The simultaneously recorded bandwidth is up to 454(1) GHz and a signal-to-noise ratio of 7.3(2) x 10$^2$ Hz$^{-1/2}$ can be reached. The conversion preserves the coherence of the d…
Fourier transform infrared (FTIR) spectrometers have been the dominant technology in the field of mid-infrared (MIR)spectroscopy for decades. Supercontinuum laser sources operating in the MIR spectral region now offer the potential to enrich the field of FTIR spectroscopy due to their distinctive properties, such as high-brightness, broadband spectral coverage and enhanced stability. In our contribution, we introduce this advanced light source as a replacement for conventional thermal emitters. Furthermore, an approach to efficient coupling of pulsed MIR supercontinuum sources to FTIR spectrom…
We present a continuous-filtering Vernier spectrometer operating in the 3.15-3.4 $μ$m range, based on a femtosecond doubly resonant optical parametric oscillator, a cavity with a finesse of 340, a grating mounted on a galvo scanner and two photodiodes. The spectrometer allows acquisition of one spectrum spanning 250 nm of bandwidth in 25 ms with 8 GHz resolution, sufficient for resolving molecular lines at atmospheric pressure. An active lock ensures good frequency and intensity stability of the consecutive spectra and enables continuous signal acquisition and efficient averaging. The relative…
We demonstrate the usefulness of a nanosecond pulsed single-mode mid-infrared (MIR) optical parametric oscillator (OPO) for Photoacoustic (PA) spectroscopic measurements. The maximum wavelength ranges for the signal and idler are 1.4 um to 1.7 um and 2.8 um to 4.6 um, respectively, and with a MIR output power of up to 500 mW. Making the OPO useful for different spectroscopic PA trace-gas measurements targeting the major market opportunity of environmental monitoring and breath gas analysis. We perform spectroscopic measurements of methane (CH4) nitrogen dioxide (NO2) and ammonia (NH3) in the 2…
We demonstrate the use of dual-comb spectroscopy for isotope ratio measurements. We show that the analysis spectral range of a free-running near-infrared dual-comb spectrometer can be extended to the mid-infrared by difference frequency generation to target specific spectral regions suitable for such measurements, and especially the relative isotopic ratio $δ{}^{13}$C. The measurements performed present a very good repeatability over several days with a standard deviation below 2$\unicode{x2030}$ for a recording time of a few tens of seconds, and the results are compatible with measurements ob…
We report on a technically simple approach to achieve high-resolution and high-sensitivity Fourier-domain OCT imaging in the mid-infrared range. The proposed OCT system employs an InF3 supercontinuum source. A specially designed dispersive scanning spectrometer based on a single InAsSb point detector is employed for detection. The spectrometer enables structural OCT imaging in the spectral range from 3140 nm to 4190 nm with a characteristic sensitivity of over 80 dB and an axial resolution below 8 um. The capabilities of the system are demonstrated for imaging of porous ceramic samples and tra…
Mid-infrared (MIR) spectrometers are invaluable tools for molecular fingerprinting and hyper-spectral imaging. Among the available spectroscopic approaches, GHz MIR dual-comb absorption spectrometers have the potential to simultaneously combine the high-speed, high spectral resolution, and broad optical bandwidth needed to accurately study complex, transient events in chemistry, combustion, and microscopy. However, such a spectrometer has not yet been demonstrated due to the lack of GHz MIR frequency combs with broad and full spectral coverage. Here, we introduce the first broadband MIR freque…
Faint light spectroscopy has many important applications such as fluorescence spectroscopy, lidar and astronomical observations. However, long measurement time limit its application on real-time measurement. In this work, a photon counting reconstructive spectrometer combining metasurfaces and superconducting nanowire single photon detectors (SNSPDs) was proposed. A prototype device was fabricated on a silicon on isolator (SOI) substrate, and its performance was characterized. Experiment results show that this device support spectral reconstruction of mono-color lights with a resolution of 2 n…
Four-wave-mixing-based quantum cascade laser frequency combs (QCL-FC) are a powerful photonic tool, driving a recent revolution in major molecular fingerprint regions, i.e. mid- and far-infrared domains. Their compact and frequency-agile design, together with their high optical power and spectral purity, promise to deliver an all-in-one source for the most challenging spectroscopic applications. Here, we demonstrate a metrological-grade hybrid dual comb spectrometer, combining the advantages of a THz QCL-FC with the accuracy and absolute frequency referencing provided by a free-standing, optic…
The large transparency window of silicon, covering the 1.1 um 8 um wavelength range, makes it a promising platform for the implementation of photothermal-based absorption spectrometers. These devices indirectly sense absorption in the mid-infrared (MIR) by using near-infrared (NIR) wavelengths, thereby enabling the realization of MIR absorption spectrometers without the need for MIR photodetectors. Nevertheless, due to their comparatively large index contrast and cross-sections, MIR Si strip waveguides are multi-mode at NIR wavelengths, hindering device implementation. Here we present, for the…
We present a dual-comb spectrometer based on two passively mode-locked waveguide lasers integrated in a single Er-doped ZBLAN chip. This original design yields two free-running frequency combs having a high level of mutual stability. We developed in parallel a self-correction algorithm that compensates residual relative fluctuations and yields mode-resolved spectra without the help of any reference laser or control system. Fluctuations are extracted directly from the interferograms using the concept of ambiguity function, which leads to a significant simplification of the instrument that will …
We have developed a dispersive spectrometer using a compact immersion grating for direct frequency comb spectroscopy in the long-wave infrared region of 8-10 μm. A frequency resolution of 463 MHz is achieved, which is the highest reported in this wavelength region with a dispersive direct frequency comb spectrometer. We also demonstrate individual mode-resolved imaging of the frequency comb spectrum by Vernier cavity filtering and apply this to obtain both simple and complex molecular spectra. These results indicate that the immersion grating spectrometer offers the next advancement for sensit…
Optical frequency combs generated by multiple four-wave mixing of two stabilized single-frequency lasers in optical fibers are proposed for use as high precision frequency markers, calibration of astrophysical spectrometers and metrology. Use of highly nonlinear and photonic crystal fibers with very short lengths and small group velocity dispersion, combined with energy and momentum conservation required by the parametric generation, assures negligible phase mismatch between comb frequencies. In contrast to combs from mode-locked lasers or microcavities, the absence of a resonator allows large…
A spectrometer for resonant inelastic X-ray scattering (RIXS) is proposed where imaging and dispersion actions in two orthogonal planes are combined to deliver full two-dimensional map of RIXS intensity in one shot with parallel detection in incoming hvin and outgoing hvout photon energies. Preliminary ray-tracing simulations with a typical undulator beamline demonstrate a resolving power well above 11000 in both hvin and hvout near a photon energy of 930 eV, with a vast potential for improvement. Combining such a spectrometer - nicknamed hv2 - with an XFEL source allows efficient time-resolve…
We demonstrate the measurement of single-shot spectra of temporally selected micropulses from a mid-infrared (MIR) free-electron laser (FEL) by upconversion. We achieve the upconversion of FEL pulses at 11 μm using externally synchronized Nd:YAG or microchip laser pulses at 1064 nm to produce sum-frequency mixing (SFM) signals at 970 nm, which are detected by a compact CCD spectrometer without an intensifier. Our experimental system is very cost-effective, and allows us to obtain the laser spectra of selected micropulses at any temporal position within a single macropulse from an oscillator-ty…
Fourier transform (FT) spectroscopy is a versatile technique for studying the infrared (IR) optical response of solid-, liquid-, and gas-phase samples. In standard FT-IR spectrometers, a light beam passing through a Michelson interferometer is focused onto a sample with condenser optics. This design enables us to examine relatively small samples, but the large solid angle of the focused infrared beam makes it difficult to analyze angle-dependent characteristics. Here we design and construct a high-precision angle-resolved reflection setup compatible with a commercial FT-IR spectrometer. Our se…
Recent years have seen the development of quantum sensing concepts utilizing nonlinear interferometers based on correlated photon pairs generated by spontaneous parametric down-conversion (SPDC). Using SPDC far from frequency degeneracy allows a 'division of labor' between the mid-infrared photon for strongest sample interaction and the correlated near-infrared photon for low-noise detection. The small number of photons provided by SPDC and the resulting inferior signal-to-noise ratio are, however, a limiting factor preventing wide applicability of the novel sensing concept. Here, we demonstra…
We demonstrate the performance of a dual frequency comb QCL spectrometer for the application of vibrational Stark spectroscopy. Measurements performed on fluorobenzene with the dual-comb spectrometer (DCS) were compared to results obtained using a conventional Fourier transform infrared (FTIR) instrument in terms of spectral response, parameter estimation, and signal-to-noise ratio. The dual-comb spectrometer provided similar qualitative and quantitative data as the FTIR setup in 250 times shorter acquisition time. For fluorobenzene, the DCS measurement resulted in a more precise estimation of…
We present a directly generated on-chip dual-comb source at THz frequencies. The multi-heterodyne beating signal of two free-running THz quantum cascade laser frequency combs is measured electrically using one of the combs as a detector, fully exploiting the unique characteristics of quantum cascade active regions. Up to 30 modes can be detected corresponding to a spectral bandwidth of 630 GHz, being the available bandwidth of the dual comb configuration. The multi-heterodyne signal is used to investigate the equidistance of the comb modes showing an accuracy of $10^{-12}$ at the carrier frequ…
A mid-Infrared frequency comb is produced via an optical parametric oscillator (OPO) pumped by an amplified 100 MHz Yb:fiber mode-locked laser. We use this source to make measurements of the concentration of the atmospherically-relevant species of CH4 and H2O over a bandwidth of 100 nm centered at 3.25 um. Multiple absorption lines for each species are detected with millisecond acquisition time using a virtually-imaged phased array (VIPA) spectrometer. The measured wavelength-dependent absorption profile is compared to and fitted by a model, yielding quantitative values of the atmospheric conc…
Fourier transform spectroscopy based on incoherent light sources is a well-established tool in research fields from molecular spectroscopy and atmospheric monitoring to material science and biophysics. It provides broadband molecular spectra and information about the molecular structure and composition of absorptive media. However, the spectral resolution is fundamentally limited by the maximum delay range (Δ$_{max}$) of the interferometer, so acquisition of high-resolution spectra implies long measurement times and large instrument size. We overcome this limit by combining the Fourier transfo…
Mid-infrared (mid-IR) spectroscopy provides a way to study structures and dynamics of complicated molecules in condensed phases. Therefore, developing compact and broadband mid-IR spectrometer has been a long-standing challenge. Here, we show that a highly coherent and broadband mid-IR frequency comb can be generated by using an intra-pulse difference-frequency-generation with a train of pulses from a few-cycle Ti:Sapphire oscillator. By tightly focusing the oscillator output beam into a single-pass fan-out-type periodically-poled lithium niobate crystal and tilting the orientation of the crys…
In the current study, a quantum-cascade-laser-based dual-comb spectrometer (DCS) was used to paint a detailed picture of a 1.0 ms high-temperature reaction between propyne and oxygen. The DCS interfaced with a shock tube to provide pre-ignition conditions of 1225 K, 2.8 atm, and 2% p-C3H4/18% O2/Ar. The spectrometer consisted of two free-running, non-stabilized frequency combs each emitting at 179 wavelengths between 1174 and 1233 cm-1. A free spectral range, f_r, of 9.86 GHz and a difference in comb spacing, Δf_r, of 5 MHz, enabled a theoretical time resolution of 0.2 us but the data was time…
The optical design of a novel spectrometer is present, combining a cylindrically convex pre-mirror with a cylindrically concave VLS grating (both in meridional) to deliver a resolving power of 100,000-200,000 in 'water window' (2-5nm). More remarkably, unlike a typical RIXS spectrometer to obtain such high resolution by tight focusing or tiny confinement slit (<1μm), here the resolution could be achieved for an effective meridional source size of 50μm (r.m.s.). The overall optical aberrations of the system are well analysed and compensated, providing an excellent flat field at the detector dom…
The impact of photodetector nonlinearity on dual-comb spectrometers is described and compared to that of Michelson-based Fourier transform spectrometers (FTS). The optical sampling occurring in the dual-comb approach, being the key difference with FTS, causes optical aliasing of the nonlinear spectral artifacts. Measured linear and nonlinear interferograms are presented to validate the model. Absorption lines of H$^{13}$CN are provided to understand the impact of nonlinearity on spectroscopic measurements.
A laser frequency combs is a broad spectrum composed of equidistant narrow lines. Initially invented for frequency metrology, such combs enable new approaches to spectroscopy over broad spectral bandwidths, of particular relevance to molecules. With optical frequency combs, the performance of existing spectrometers, such as Michelson-based Fourier transform interferometers or crossed dispersers, involving e.g. virtual imaging phase array (VIPA) étalons, is dramatically enhanced. Novel types of instruments, such as dual-comb spectrometers, lead to a new class of devices without moving parts for…
Two frequency combs can be used to measure the full complex response of a sample in a configuration which can be alternatively viewed as the equivalent of a dispersive Fourier transform spectrometer, infrared time domain spectrometer, or a multiheterodyne laser spectrometer. This dual comb spectrometer retains the frequency accuracy and resolution inherent to the comb sources. We discuss, in detail, the specific design of our coherent dual-comb spectrometer and demonstrate the potential of this technique by measuring the first overtone vibration of hydrogen cyanide, centered at 194 THz (1545 n…
Fast (sub-second) spectroscopy with high spectral resolution is of vital importance for revealing quantum chemistry kinetics of complex chemical and biological reactions. Fourier transform (FT) spectrometers can achieve high spectral resolution and operate at hundreds of ms time scales in rapid-scan mode. However, the linear translation of a scanning mirror imposes stringent time-resolution limitations to these systems, which makes simultaneous high spectral and temporal resolution impossible. Here, we demonstrate an FT spectrometer whose operational principle is based on continuous rotational…
The quest for extrasolar planets and their characterisation as well as studies of fundamental physics on cosmological scales rely on capabilities of high-resolution astronomical spectroscopy. A central requirement is a precise wavelength calibration of astronomical spectrographs allowing for extraction of subtle wavelength shifts from the spectra of stars and quasars. Here, we present an all-fibre, 400 nm wide near-infrared frequency comb based on electro-optic modulation with 14.5 GHz comb line spacing. Tests on the high-resolution, near-infrared spectrometer GIANO-B show a photon-noise limit…
Compact spectrometers based on disordered planar waveguides exhibit a rather high resolution with a relatively small footprint as compared to conventional spectrometers. This is achieved by multiple scattering of light which - if properly engineered - significantly enhances the effective optical path length. Here a design study of random spectrometers for TE- and TM-polarized light is presented that combines the results of Mie theory, multiple-scattering theory and full electromagnetic simulations. It is shown that the performance of such random spectrometers depends on single scattering quant…
Mid-infrared dual-comb spectroscopy has the potential to supplant conventional high-resolution Fourier transform spectroscopy in applications that require high resolution, accuracy, signal-to-noise ratio, and speed. Until now, dual-comb spectroscopy in the mid-infrared has been limited to narrow optical bandwidths or to low signal-to-noise ratios. Using a combination of digital signal processing and broadband frequency conversion in waveguides, we demonstrate a mid-infrared dual-comb spectrometer that can measure comb-tooth resolved spectra across an octave of bandwidth in the mid-infrared fro…
Dual comb spectroscopy (DCS) is a broadband technique offering high resolution and fast data acquisition. We describe a hybrid dual comb spectrometer comprising a broadband commercial fiber laser system offering a wide range of sample interrogation, and an actively mode locked semiconductor laser (MLL) having a widely tunable, relatively narrow spectrum. The mutual coherence over 100 seconds has been realized between the two combs. We employed the DCS system to characterize the absorption spectrum of rubidium atoms at 313 K with a high signal to noise ratio. The broadband laser is directly loc…
Continuous Wave (CW) Terahertz spectroscopy enabled by photomixing is a promising high precision spectroscopic tool for the examination of a wide variety of samples including biological, chemical, and solid state. However, often it would be of interest to examine isolated samples free from bulk effects that broaden spectral features. In this form samples with low concentrations of absorbers have a reduced cross section making coupling to an external driving field a challenge. By utilising THz metamaterials one can borrow the concepts of surface enhanced Raman spectroscopy to confine and concen…
We report on our ongoing effort to measure the Boltzmann constant, $k_B,$ using the Doppler broadening technique on ammonia. This paper presents some of the improvements made to the mid-infrared spectrometer including the use of a phase-stabilized quantum cascade laser, a lineshape analysis based on a refined physical model and an improved fitting program 2 increasing the confidence in our estimates of the relevant molecular parameters, and a first evaluation of the saturation parameter and its impact on the measurement of k B. A summary of the systematic effects contributing to the measuremen…
