Near-ultraviolet photon-counting dual-comb spectroscopy.

Ultraviolet spectroscopy provides unique insights into the structure of matter with applications ranging from fundamental tests to photochemistry in the Earth's atmosphere and astronomical observations from space telescopes1-8. At longer wavelengths, dual-comb spectroscopy, using two interfering laser frequency combs, has become a powerful technique capable of simultaneously providing a broad spectral range and very high resolution9. Here we demonstrate a photon-counting approach that can extend the unique advantages of this method into ultraviolet regions where nonlinear frequency conversion tends to be very inefficient. Our spectrometer, based on two frequency combs with slightly different repetition frequencies, provides a wide-span, high-resolution frequency calibration within the accuracy of an atomic clock, and overall consistency of the spectra. We demonstrate a signal-to-noise ratio at the quantum limit and an optimal use of the measurement time, provided by the multiplexed recording of all spectral data on a single photon-counter10. Our initial experiments are performed in the near-ultraviolet and in the visible spectral ranges with alkali-atom vapour, with a power per comb line as low as a femtowatt. This crucial step towards precision broadband spectroscopy at short wavelengths paves the way for extreme-ultraviolet dual-comb spectroscopy, and, more generally, opens up a new realm of applications for photon-level diagnostics, as encountered, for example, when driving single atoms or molecules.

Photon-level broadband spectroscopy and interferometry with two frequency combs.

We probe complex optical spectra at high resolution over a broad span in almost complete darkness. Using a single photon-counting detector at light power levels that are a billion times weaker than commonly employed, we observe interferences in the counting statistics with two separate mode-locked femtosecond lasers of slightly different repetition frequencies, each emitting a comb of evenly spaced spectral lines over a wide spectral span. Unique advantages of the emerging technique of dual-comb spectroscopy, such as multiplex data acquisition with many comb lines, potential very high resolution, and calibration of the frequency scale with an atomic clock, can thus be maintained for scenarios where only few detectable photons can be expected. Prospects include spectroscopy of weak scattered light over long distances, fluorescence spectroscopy of single trapped atoms or molecules, or studies in the extreme-ultraviolet or even soft-X-ray region with comb sources of low photon yield. Our approach defies intuitive interpretations in a picture of photons that exist before detection.

Mid-infrared feed-forward dual-comb spectroscopy.

Mid-infrared high-resolution spectroscopy has proven an invaluable tool for the study of the structure and dynamics of molecules in the gas phase. The advent of frequency combs advances the frontiers of precise molecular spectroscopy. Here we demonstrate, in the important 3-µm spectral region of the fundamental CH stretch in molecules, dual-comb spectroscopy with experimental coherence times between the combs that exceed half an hour. Mid-infrared Fourier transform spectroscopy using two frequency combs with self-calibration of the frequency scale, negligible contribution of the instrumental line shape to the spectral profiles, high signal-to-noise ratio, and broad spectral bandwidth opens up opportunities for precision spectroscopy of small molecules. Highly multiplexed metrology of line shapes may be envisioned.

Time-resolved dual-comb spectroscopy with a single electro-optic modulator.

Time-resolved near-infrared absorption spectroscopy of single non-repeatable transient events is performed at high spectral resolution with a dual-comb interferometer using a continuous-wave laser followed by a single electro-optic amplitude modulator. By sharing high-speed electrical/optical components, our spectrometer greatly simplifies the implementation of dual-comb spectroscopy and offers a high mutual coherence time, measured up to 50 s, without any active stabilization system and/or data processing. The time resolution is as short as 100 µs in our experimental demonstration. For a span of 36 GHz, the mean signal-to-noise ratio of 80, at 100-MHz spectral resolution and 100-µs measurement time, enables precise determination of the parameters of rovibrational lines, including intensity or concentration.

An unstabilized femtosecond semiconductor laser for dual-comb spectroscopy of acetylene.

Dual-comb systems based on two optical frequency combs of slightly different line spacing emerge as powerful tools in spectroscopy and interferometry. Semiconductor lasers have a high impact in continuous-wave tunable laser spectroscopy. Here we demonstrate the first dual-comb interferometer based on a single femtosecond semiconductor laser: a dual-comb modelocked optically pumped external-cavity surface-emitting laser (MIXSEL) ideally suited for a 1 to 10 GHz comb spacing. At a center wavelength of 1.03 µm (9709 cm-1) we measured acetylene gas transmittance with a resolution of 2.7 GHz in 100 ms with residual errors of less than 3% using thousand comb lines without aliasing effects.

Supercontinuum generation in angle-etched diamond waveguides.

We experimentally demonstrate on-chip supercontinuum generation in the visible region in angle-etched diamond waveguides. We measure an output spectrum spanning 670-920 nm in a 5-mm-long waveguide using 100-fs pulses with 187 pJ of incident pulse energy. Our fabrication technique, combined with diamond's broad transparency window, offers a potential route toward broadband supercontinuum generation in the UV domain.

Coherent Raman spectro-imaging with laser frequency combs.

Advances in optical spectroscopy and microscopy have had a profound impact throughout the physical, chemical and biological sciences. One example is coherent Raman spectroscopy, a versatile technique interrogating vibrational transitions in molecules. It offers high spatial resolution and three-dimensional sectioning capabilities that make it a label-free tool for the non-destructive and chemically selective probing of complex systems. Indeed, single-colour Raman bands have been imaged in biological tissue at video rates by using ultra-short-pulse lasers. However, identifying multiple, and possibly unknown, molecules requires broad spectral bandwidth and high resolution. Moderate spectral spans combined with high-speed acquisition are now within reach using multichannel detection or frequency-swept laser beams. Laser frequency combs are finding increasing use for broadband molecular linear absorption spectroscopy. Here we show, by exploring their potential for nonlinear spectroscopy, that they can be harnessed for coherent anti-Stokes Raman spectroscopy and spectro-imaging. The method uses two combs and can simultaneously measure, on the microsecond timescale, all spectral elements over a wide bandwidth and with high resolution on a single photodetector. Although the overall measurement time in our proof-of-principle experiments is limited by the waiting times between successive spectral acquisitions, this limitation can be overcome with further system development. We therefore expect that our approach of using laser frequency combs will not only enable new applications for nonlinear microscopy but also benefit other nonlinear spectroscopic techniques.

Doppler-free Fourier transform spectroscopy.

Sub-Doppler broadband multi-heterodyne spectroscopy is proposed and experimentally demonstrated. Using two laser frequency combs of slightly different repetition frequencies, we have recorded Doppler-free two-photon dual-comb spectra of atomic rubidium resonances of a width of 6 MHz, while simultaneously interrogating a spectral span of 10 THz. The atomic transitions are uniquely identified via the intensity modulation of the observed fluorescence radiation. To the best of our knowledge, these results represent the first demonstration of Doppler-free Fourier transform spectroscopy and extend the range of applications of broadband spectroscopy towards precision nonlinear spectroscopy.

Dual-comb coherent Raman spectroscopy with lasers of 1-GHz pulse repetition frequency.

We extend the technique of multiplex coherent Raman spectroscopy with two femtosecond mode-locked lasers to oscillators of a pulse repetition frequency of 1 GHz. We demonstrate a spectra of liquids, which span 1100 cm-1 of Raman shifts. At a resolution of 6 cm-1, their measurement time may be as short as 5 µs for a refresh rate of 2 kHz. The waiting period between acquisitions is improved 10-fold compared to previous experiments with two lasers of 100-MHz repetition frequencies.

Dual-comb thin-disk oscillator.

Dual-comb spectroscopy (DCS) normally operates with two independent, relatively low power and actively synchronized laser sources. This hinders the wide adoption for practical implementations and frequency conversion into deep UV and VUV spectral ranges. Here, we report a fully passive, high power dual-comb laser based on thin-disk technology and its application to direct frequency comb spectroscopy. The peak power (1.2 MW) and the average power (15 W) of our Yb:YAG thin-disk dual-comb system are more than one-order-of-magnitude higher than in any previous systems. The scheme allows easy adjustment of the repetition frequency difference during operation. Both combs share all cavity components which leads to an excellent mutual stability. A time-domain signal recorded over 10 ms without any active stabilization was sufficient to resolve individual comb lines after Fourier transformation.

Cr : YAG chirped-pulse oscillator.

We demonstrate chirped-pulse operation of a Cr : YAG passively mode-locked laser. Different operation regimes of the laser are extensively investigated in the vicinity of zero dispersion both experimentally and numerically. It is shown that for a given laser configuration, transition to the positive dispersion regime allows a 5-fold increase in the output pulse energy, which is otherwise limited by the onset of the multipulsing or 'chaotic' mode-locking. The output pulses have 1.4 ps duration and are compressible down to 120 fs in a 3 m piece of silica fiber, enabling supercontinuum generation in a nonlinear fiber. The spectrum shape and operation stability of the chirped-pulse regime depend strongly on the amount and shape of the intracavity dispersion. The numerical model predicts the existence of the minimum amount of the positive dispersion, above which the chirped-pulse regime can be realized. Once located, the chirped-pulse regime can be reliably reproduced and is sufficiently stable for applications.

A phase-stable dual-comb interferometer.

Laser frequency combs emit a spectrum with hundreds of thousands of evenly spaced phase-coherent narrow lines. A comb-enabled instrument, the dual-comb interferometer, exploits interference between two frequency combs and attracts considerable interest in precision spectroscopy and sensing, distance metrology, tomography, telecommunications, etc. Mutual coherence between the two combs over the measurement time is a pre-requisite to interferometry, although it is instrumentally challenging. At best, the mutual coherence reaches about 1 s. Computer-based phase-correction techniques, which often lead to artifacts and worsened precision, must be implemented for longer averaging times. Here with feed-forward relative stabilization of the carrier-envelope offset frequencies, we experimentally realize a mutual coherence over times approaching 2000 s, more than three orders of magnitude longer than that of state-of-the-art dual-comb systems. An illustration is given with near-infrared Fourier transform molecular spectroscopy with two combs of slightly different repetition frequencies. Our technique without phase correction can be implemented with any frequency comb generator including microresonators or semiconductor lasers.

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.

Mid-infrared dual-comb spectroscopy with electro-optic modulators.

Absorption spectroscopy of fundamental ro-vibrational transitions in the mid-infrared region provides a powerful tool for studying the structure and dynamics of molecules in the gas phase and for sensitive and quantitative gas sensing. Laser frequency combs permit novel approaches to perform broadband molecular spectroscopy. Multiplex dual-comb spectroscopy without moving parts can achieve particularly high speed, sensitivity and resolution. However, achieving Doppler-limited resolution in the mid-infrared still requires overcoming instrumental challenges. Here we demonstrate a new approach based on difference-frequency generation of frequency-agile near-infrared frequency combs that are produced using electro-optic modulators. The combs have a remarkably flat intensity distribution, and their positions and line spacings can be freely selected by simply dialing a knob. Using the proposed technique, we record, in the 3-µm region, Doppler-limited absorption spectra with resolved comb lines within milliseconds, and precise molecular line parameters are retrieved. Our technique holds promise for fast and sensitive time-resolved studies of, for example, trace gases.

Roadmap on optical sensors.

Sensors are devices or systems able to detect, measure and convert magnitudes from any domain to an electrical one. Using light as a probe for optical sensing is one of the most efficient approaches for this purpose. The history of optical sensing using some methods based on absorbance, emissive and florescence properties date back to the 16th century. The field of optical sensors evolved during the following centuries, but it did not achieve maturity until the demonstration of the first laser in 1960. The unique properties of laser light become particularly important in the case of laser-based sensors, whose operation is entirely based upon the direct detection of laser light itself, without relying on any additional mediating device. However, compared with freely propagating light beams, artificially engineered optical fields are in increasing demand for probing samples with very small sizes and/or weak light-matter interaction. Optical fiber sensors constitute a subarea of optical sensors in which fiber technologies are employed. Different types of specialty and photonic crystal fibers provide improved performance and novel sensing concepts. Actually, structurization with wavelength or subwavelength feature size appears as the most efficient way to enhance sensor sensitivity and its detection limit. This leads to the area of micro- and nano-engineered optical sensors. It is expected that the combination of better fabrication techniques and new physical effects may open new and fascinating opportunities in this area. This roadmap on optical sensors addresses different technologies and application areas of the field. Fourteen contributions authored by experts from both industry and academia provide insights into the current state-of-the-art and the challenges faced by researchers currently. Two sections of this paper provide an overview of laser-based and frequency comb-based sensors. Three sections address the area of optical fiber sensors, encompassing both conventional, specialty and photonic crystal fibers. Several other sections are dedicated to micro- and nano-engineered sensors, including whispering-gallery mode and plasmonic sensors. The uses of optical sensors in chemical, biological and biomedical areas are described in other sections. Different approaches required to satisfy applications at visible, infrared and THz spectral regions are also discussed. Advances in science and technology required to meet challenges faced in each of these areas are addressed, together with suggestions on how the field could evolve in the near future.

Acetylene weak bands at 2.5 µm from intracavity Cr:ZnSe laser absorption observed with time-resolved Fourier transform spectroscopy.

The spectral dynamics of a mid-infrared multimode Cr(2+):ZnSe laser located in a vacuum sealed chamber containing acetylene at low pressure is analyzed by a stepping-mode high-resolution time-resolved Fourier transform interferometer. Doppler-limited absorption spectra of C(2)H(2) in natural isotopic abundance are recorded around 4000 cm(-1) with kilometric absorption path lengths and sensitivities better than 3 10(-8) cm(-1). Two cold bands are newly identified and assigned to the ν(1)+ν(4) (1) and ν(3)+ν(5) (1) transitions of (12)C(13)CH(2). The ν(1)+ν(5) (1) band of (12)C(2)HD and fourteen (12)C(2)H(2) bands are observed, among which for the first time ν(2)+2ν(4) (2)+ν(5) (-1).

An octave-spanning mid-infrared frequency comb generated in a silicon nanophotonic wire waveguide.

Laser frequency combs, sources with a spectrum consisting of hundred thousands evenly spaced narrow lines, have an exhilarating potential for new approaches to molecular spectroscopy and sensing in the mid-infrared region. The generation of such broadband coherent sources is presently under active exploration. Technical challenges have slowed down such developments. Identifying a versatile highly nonlinear medium for significantly broadening a mid-infrared comb spectrum remains challenging. Here we take a different approach to spectral broadening of mid-infrared frequency combs and investigate CMOS-compatible highly nonlinear dispersion-engineered silicon nanophotonic waveguides on a silicon-on-insulator chip. We record octave-spanning (1,500-3,300 nm) spectra with a coupled input pulse energy as low as 16 pJ. We demonstrate phase-coherent comb spectra broadened on a room-temperature-operating CMOS-compatible chip.

Adaptive real-time dual-comb spectroscopy.

The spectrum of a laser frequency comb consists of several hundred thousand equally spaced lines over a broad spectral bandwidth. Such frequency combs have revolutionized optical frequency metrology and they now hold much promise for significant advances in a growing number of applications including molecular spectroscopy. Despite an intriguing potential for the measurement of molecular spectra spanning tens of nanometres within tens of microseconds at Doppler-limited resolution, the development of dual-comb spectroscopy is hindered by the demanding stability requirements of the laser combs. Here we overcome this difficulty and experimentally demonstrate a concept of real-time dual-comb spectroscopy, which compensates for laser instabilities by electronic signal processing. It only uses free-running mode-locked lasers without any phase-lock electronics. We record spectra spanning the full bandwidth of near-infrared fibre lasers with Doppler-limited line profiles highly suitable for measurements of concentrations or line intensities. Our new technique of adaptive dual-comb spectroscopy offers a powerful transdisciplinary instrument for analytical sciences.

Few-cycle, broadband, mid-infrared optical parametric oscillator pumped by a 20-fs Ti:sapphire laser.

A few-cycle, broadband, singly-resonant optical parametric oscillator (OPO) for the mid-infrared based on MgO-doped periodically-poled LiNbO3 (MgO:PPLN), synchronously pumped by a 20-fs Ti:sapphire laser is reported. By using crystal interaction lengths as short as 250 µm, and careful dispersion management of input pump pulses and the OPO resonator, near-transform-limited, few-cycle idler pulses tunable across the mid-infrared have been generated, with as few as 3.7 optical cycles at 2682 nm. The OPO can be continuously tuned over 2179-3732 nm (4589-2680 cm-1) by cavity delay tuning, providing up to 33 mW of output power at 3723 nm. The idler spectra exhibit stable broadband profiles with bandwidths spanning over 422 nm (FWHM) recorded at 3732 nm. The effect of crystal length on spectral bandwidth and pulse duration is investigated at a fixed wavelength, confirming near-transform-limited idler pulses for all grating interaction lengths. By locking the repetition frequency of the pump laser to a radio-frequency reference, and without active stabilization of the OPO cavity length, an idler power stability better than 1.6% rms over >2.75 hours is obtained when operating at maximum output power, in excellent spatial beam quality with TEM00 mode profile. Photograph shows a multigrating MgO:PPLN crystal used as a nonlinear gain medium in the few-cycle femtosecond mid-IR OPO. The visible light is the result of non-phase-matched sum-frequency mixing between the interacting beams.

Supercontinua for high-resolution absorption multiplex infrared spectroscopy.

Supercontinua generated in highly nonlinear fibers by ultrashort-pulse lasers can be used for high-resolution Fourier transform absorption spectroscopy. The practical advantages of these bright ultrabroadband light sources for spectroscopy in the near-infrared region are reported. A Cr(4+):YAG femtosecond laser broadened by an extruded soft-glass photonic crystal fiber, emitting from 1200 to 2200 nm and from 675 to 950 nm, provides a spectral radiance 1 x 10(5) times higher than that of a 3000 K blackbody and 10(2) times higher than that of synchrotron radiation. The C(2)H(2) and NH(3) overtone spectra are recorded by using this source within a few seconds.