mid-IR Quantum Cascade Lasers Research Articles

Active Region Overheating in Pulsed Quantum Cascade Lasers: Effects of Nonequilibrium Heat Dissipation on Laser Performance

Mid IR Quantum cascade lasers are of high interest for the scientific community due to their unique applications. However, the QCL designs require careful engineering to overcome some crucial disadvantages. One of them is active region (ARn) overheating, which significantly affects laser characteristics, even in the pulsed mode. In this work, we consider the effects related to the nonequilibrium temperature distribution when thermal resistance formalism is irrelevant. We employ the heat equation and discuss the possible limitations and structural features stemming from the chemical composition of the ARn. We show that the presence of solid solutions in the ARn structure fundamentally limits the heat dissipation in pulsed and CW regimes due to their low thermal conductivity compared with binary compounds. Also, the QCL postgrowths affect the thermal properties of a device closer to CW mode, while it is by far less important in the short-pulsed mode.

SI-traceable validation of a laser spectrometer for balloon-borne measurements of water vapor in the upper atmosphere

Abstract. Despite its crucial role in the Earth's radiative balance, upper-air water vapor (H2O) is still lacking accurate, in situ, and continuous monitoring. Especially in the upper troposphere–lower stratosphere (UTLS), these measurements are notoriously difficult, and significant discrepancies have been reported in the past between different measuring techniques. Here, we present a laboratory assessment of a recently developed mid-IR quantum-cascade laser absorption spectrometer, called ALBATROSS, for balloon-borne measurements of H2O in the UTLS. The validation was performed using SI-traceable reference gas mixtures generated based on the permeation method and dynamic dilution. The accuracy and precision of ALBATROSS were evaluated at a wide range of pressures (30–250 mbar) and H2O amount fractions (2.5–35 ppm), representative of the atmospheric variability in H2O in the UTLS. The best agreement was achieved by implementing a quadratic speed-dependent Voigt profile (qSDVP) line shape model in the spectroscopic retrieval algorithm. The molecular parameters required by this parameterization were determined empirically using a multi-spectrum fitting approach over different pressure conditions. In the laboratory environment, ALBATROSS achieves an accuracy better than ±1.5 % with respect to the SI-traceable reference at all investigated pressures and H2O amount fractions. The measurement precision was found to be better than 30 ppb (i.e., 0.1 % at 35 ppm H2O) at 1 s resolution for all conditions. This performance, unprecedented for a balloon-borne hygrometer, demonstrates the exceptional potential of mid-IR laser absorption spectroscopy as a new reference method for in situ measurements of H2O in the UTLS.

Efficient strain-modified improved nonparabolic-band energy dispersion model that considers the effect of conduction band nonparabolicity in mid-infrared quantum cascade lasers.

Intersubband polar-optical-phonon (POP) scattering plays an important role in determining the population inversion and optical gain of mid-infrared (mid-IR) quantum cascade lasers (QCLs). In particular, the nonparabolicity of the conduction band (CB) significantly affects the energy dispersion relation and intersubband POP scattering time. However, the currently used parabolic-band (PB) and nonparabolic-band (NPB) energy dispersion models are not appropriate for mid-IR QCLs because they are unsuitable for high electron wave vectors and do not consider the effect of applied strain on the energy dispersion relation of the CB. The eight-band k·p method can provide a relatively accurate nonparabolic energy dispersion relation for high electron wave vectors but has the disadvantages of high computational complexity and spurious solutions to be discarded. Consequently, we propose a strain-modified improved nonparabolic-band (INPB) energy dispersion model that has no spurious solution and acceptable accuracy, compared to the eight-band k·p method. To demonstrate the accuracy and efficiency of our proposed INPB model compared with those of the PB, NPB, and eight-band k·p models, we calculate the energy dispersion relations and intersubband POP scattering times in a strain-compensated QCL with a lasing wavelength of 3.58 µm. Calculation results reveal that our proposed model is almost as accurate as the eight-band k·p model; however, it enables much faster calculations and is free from spurious solutions.

Inversionless terahertz lasing in a four-level Raman-type scheme within mid-infrared quantum cascade structures

This paper applies the density matrix formalism to investigate a feasibility of inversionless terahertz (THz) lasing within a mid-infrared (mid-IR) quantum cascade laser (QCL). The proposed structure aims to use a mid-IR QCL as an efficient pump source that integrated with a four-level Raman-type scheme to generate THz radiation through strong coherence excited in the system. A key aspect of the design is that the THz generation is achieved by interplay between inversion-based lasing and coherent effects due to quantum interference between the microscopic polarizations of the dipole-allowed transitions in the four-level system. THz intensity gain arising from both the inversion-based lasing and coherent effects is derived from the off-diagonal density matrix elements in the four-level system. The simulation results indicate that the proposed design demonstrates the potential to achieve THz lasing with good temperature characteristics and without the need for population inversion.

Self-consistent simulations of intracavity terahertz comb difference frequency generation by mid-infrared quantum cascade lasers

Portable terahertz (THz) frequency comb sources are highly desired for applications in rotational molecular spectroscopy and sensing. To date, direct THz quantum cascade laser (QCL) frequency comb generation is not achievable at room temperature. However, THz comb generation based on intracavity difference frequency generation (DFG) in mid-infrared (mid-IR) QCLs is a promising alternative. Here, we present a numerical study of THz DFG-QCL comb formation in mid-IR QCLs based on a self-consistent multi-domain simulation approach. The dynamical simulations are performed using our open-source software tool mbsolve, which provides a flexible and efficient codebase for solving the generalized full-wave Maxwell–Bloch equations. Here, DFG in the active region of a dual-wavelength mid-IR QCL is considered for the generation of THz radiation. The mixing process and, thus, THz generation require a high second-order intersubband nonlinear susceptibility in the QCL active region and can be obtained by targeted quantum engineering. The associated nonlinear effects are included in the Hamiltonian of our Maxwell–Bloch simulation approach. All necessary input parameters for the description of the quantum system are determined self-consistently using our in-house ensemble Monte Carlo software tool for stationary carrier transport simulations. Notably, such simulations require a full-wave Maxwell–Bloch solver that does not employ the common rotating wave approximation, as a broadband optical field extending from the THz to the mid-IR region is investigated. Our modeling approach and the obtained simulation results for two THz DFG-QCL comb setups are validated against experimental data, showing reasonable agreement. Furthermore, we obtain a locked frequency modulated comb state for mid-IR and THz regimes.

Low intensity saturation of an ISB transition by a mid-IR quantum cascade laser

We demonstrate that absorption saturation of a mid-infrared intersubband transition can be engineered to occur at moderate light intensities of the order of 10–20 kW cm−2 and at room temperature. The structure consists of an array of metal–semiconductor–metal patches hosting a judiciously designed 253 nm thick GaAs/AlGaAs semiconductor heterostructure. At low incident intensity, the structure operates in the strong light–matter coupling regime and exhibits two absorption peaks at wavelengths close to 8.9 μm. Saturation appears as a transition to the weak coupling regime—and therefore, to a single-peaked absorption—when increasing the incident intensity. Comparison with a coupled mode theory model explains the data and permits to infer the relevant system parameters. When the pump laser is tuned at the cavity frequency, the reflectivity decreases with increasing incident intensity. When instead the laser is tuned at the polariton frequencies, the reflectivity non-linearly increases with increasing incident intensity. At those wavelengths, the system, therefore, mimics the behavior of a saturable absorption mirror in the mid-IR range, a technology that is currently missing.

Rovibrational Spectroscopy of Trans and Cis Conformers of 2-Furfural from High-Resolution Fourier Transform and QCL Infrared Measurements.

The ortho-isomer 2-furfural (2-FF), which is a primary atmospheric pollutant produced from biomass combustion, is also involved in oxidation processes leading to the formation of secondary organic aerosols. Its contribution to radiative forcing remains poorly understood. Thus, monitoring 2-FF directly in the atmosphere or in atmospheric simulation chambers to characterize its reactivity is merited. The present study reports an extensive jet-cooled rovibrational study of trans and cis conformers of 2-FF in the mid-IR region using two complementary setups: a continuous supersonic jet coupled to a high-resolution Fourier transform spectrometer on the IR beamline of the SOLEIL synchrotron (JET-AILES), and a pulsed jet coupled to a mid-IR tunable quantum cascade laser spectrometer (SPIRALES). Firstly, jet-cooled spectra recorded at rotational temperatures ranging between 20 and 50 K were exploited to derive reliable excited-state molecular parameters of trans- and cis-2-FF vibrational bands in the fingerprint region. The parameters were obtained from global fits of 11,376 and 3355 lines distributed over eight and three vibrational states (including the ground state), respectively, with a root mean square of 12 MHz. In a second step, the middle resolution spectrum of 2-FF recorded at 298.15 K and available in the HITRAN database was reconstructed by extrapolating the data derived from our low-temperature high-resolution analyses to determine the cross sections of each vibrational band of both 2-FF conformers in the 700-1800 cm-1 region. Finally, we clearly demonstrated that the contribution of hot bands observed in the room temperature 2-FF spectrum, estimated between 40 and 63% of the fundamental band, must be imperatively introduced in our simulation to correctly reproduce the HITRAN vibrational cross sections of 2-FF with a deviation smaller than 10%.

Ppb-level mid-IR quartz-enhanced photoacoustic sensor for sarin simulant detection using a T-shaped tuning fork

A ppb-level mid-IR quartz-enhanced photoacoustic sensor for the highly sensitive detection of dimethyl methyl phosphonate (DMMP) —the sarin simulant—is developed using a T-shaped tuning fork. The sensor employs a narrow-linewidth mid-IR quantum cascade laser (QCL) to target a strong, interference-free DMMP absorption band. A custom quartz tuning fork with 800-μm prong spacing is employed to avoid significant photothermal noise, thus removing the requirement for an optical spatial filter. The performance of the photoacoustic sensor was optimized in terms of exciting power, modulation frequency, and gas pressure. A minimum detection limit of 6 ppb was achieved at an integration time of 300 ms, which can be further improved to 0.45 ppb at the optimal integration time of 20 s

Mid-IR quantum cascade laser spectroscopy to resolve lipid dynamics during the photocycle of bacteriorhodopsin.

Membranes are crucial for the functionality of membrane proteins in several cellular processes. Time-resolved infrared (IR) spectroscopy enables the investigation of interaction-induced dynamics of the protein and the lipid membrane. The photoreceptor and proton pump bacteriorhodopsin (BR) was reconstituted into liposomes, mimicking the native purple membrane. By utilization of deuterated lipid alkyl chains, corresponding vibrational modes are frequency-shifted into a spectrally silent window that allows us to monitor lipid dynamics during the photoreaction of BR. Our home-built quantum cascade laser (QCL)-based IR spectrometer covers all relevant spectral regions to detect both lipid and protein vibrational modes. QCL-probed transients at single wavenumbers are compared with the previously performed step-scan Fourier-transform IR measurements. The absorbance changes of the lipids could be resolved by QCL-measurements with a much better signal-to-noise ratio and with nanosecond time resolution. We found a correlation of the lipid dynamics with the protonation dynamics in the M intermediate. QCL spectroscopy extends the study of the protein's photocycle toward dynamics of the interacting membrane.

Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy.

Intramolecular or position-specific carbon isotope analysis of propane (13CH3-12CH2-12CH3 and 12CH3-13CH2-12CH3) provides unique insights into its formation mechanism and temperature history. The unambiguous detection of such carbon isotopic distributions with currently established methods is challenging due to the complexity of the technique and the tedious sample preparation. We present a direct and nondestructive analytical technique to quantify the two singly substituted, terminal (13Ct) and central (13Cc), propane isotopomers, based on quantum cascade laser absorption spectroscopy. The required spectral information on the propane isotopomers was first obtained using a high-resolution Fourier-transform infrared (FTIR) spectrometer and then used to select suitable mid-infrared regions with minimal spectral interference to obtain the optimum sensitivity and selectivity. We then measured high-resolution spectra around 1384 cm-1 of both singly substituted isotopomers by mid-IR quantum cascade laser absorption spectroscopy using a Stirling-cooled segmented circular multipass cell (SC-MPC). The spectra of the pure propane isotopomers were acquired at both 300 and 155 K and served as spectral templates to quantify samples with different levels of 13C at the central (c) and terminal (t) positions. A prerequisite for the precision using this reference template fitting method is a good match of amount fraction and pressure between the sample and templates. For samples at natural abundance, we achieved a precision of 0.33 ‰ for δ13Ct and 0.73 ‰ for δ13Cc values within 100 s integration time. This is the first demonstration of site-specific high-precision measurements of isotopically substituted non-methane hydrocarbons using laser absorption spectroscopy. The versatility of this analytical approach may open up new opportunities for the study of isotopic distribution of other organic compounds.

Rapid Detection of Accelerants in Fire Debris Using a Field Portable Mid-Infrared Quantum Cascade Laser Based Analyzer

Arson presents a challenging crime scene for fire investigators worldwide. Key to the investigation of suspected arson cases is the analysis of fire debris for the presence of accelerants or ignitable liquids. This study has investigated the application and method development of vapor phase mid-Infrared (mid-IR) spectroscopy using a field portable quantum cascade laser (QCL) based system for the detection and identification of accelerant residues such as gasoline, diesel, and ethanol in fire debris. A searchable spectral library of various ignitable fluids and fuel components measured in the vapor phase was constructed that allowed for real-time identification of accelerants present in samples using software developed in-house. Measurement of vapors collected from paper material that had been doused with an accelerant followed by controlled burning and then extinguished with water showed that positive identification could be achieved for gasoline, diesel, and ethanol. This vapor phase mid-IR QCL method is rapid, easy to use, and has the sensitivity and discrimination capability that make it well suited for non-destructive crime scene sample analysis. Sampling and measurement can be performed in minutes with this 7.5 kg instrument. This vibrational spectroscopic method required no time-consuming sample pretreatment or complicated solvent extraction procedure. The results of this initial feasibility study demonstrate that this portable fire debris analyzer would greatly benefit arson investigators performing analysis on-site.

Characterization of noise regimes in mid-IR free-space optical communication based on quantum cascade lasers.

The recent development of Quantum Cascade Lasers (QCLs) represents one of the biggest opportunities for the deployment of a new class of Free Space Optical (FSO) communication systems working in the mid-infrared (mid-IR) wavelength range. As compared to more common FSO systems exploiting the telecom range, the larger wavelength employed in mid-IR systems delivers exceptional benefits in case of adverse atmospheric conditions, as the reduced scattering rate strongly suppresses detrimental effects on the FSO link length given by the presence of rain, dust, fog, and haze. In this work, we use a novel FSO testbed operating at 4.7 µm, to provide a detailed experimental analysis of noise regimes that could occur in realistic FSO mid-IR systems based on QCLs. Our analysis reveals the existence of two distinct noise regions, corresponding to different realistic channel attenuation conditions, which are precisely controlled in our setup. To relate our results with real outdoor configurations, we combine experimental data with predictions of an atmospheric channel loss model, finding that error-free communication could be attained for effective distances up to 8 km in low visibility conditions of 1 km. Our analysis of noise regimes may have a key relevance for the development of novel, long-range FSO communication systems based on mid-IR QCL sources.

Refined modelling of anisotropy influence on the optical gain in Mid-IR quantum cascade lasers

Refined modelling of anisotropy influence on the optical gain in Mid-IR quantum cascade lasers

Identification, monitoring, and reaction kinetics of reactive trace species using time-resolved mid-infrared quantum cascade laser absorption spectroscopy: development, characterisation, and initial results for the CH<sub>2</sub>OO Criegee intermediate

Abstract. The chemistry and reaction kinetics of reactive species dominate changes to the composition of complex chemical systems, including Earth's atmosphere. Laboratory experiments to identify reactive species and their reaction products, and to monitor their reaction kinetics and product yields, are key to our understanding of complex systems. In this work we describe the development and characterisation of an experiment using laser flash photolysis coupled with time-resolved mid-infrared (mid-IR) quantum cascade laser (QCL) absorption spectroscopy, with initial results reported for measurements of the infrared spectrum, kinetics, and product yields for the reaction of the CH2OO Criegee intermediate with SO2. The instrument presented has high spectral (< 0.004 cm−1) and temporal (< 5 µs) resolution and is able to monitor kinetics with a dynamic range to at least 20 000 s−1. Results obtained at 298 K and pressures between 20 and 100 Torr gave a rate coefficient for the reaction of CH2OO with SO2 of (3.83 ± 0.63) × 10−11 cm3 s−1, which compares well to the current IUPAC recommendation of 3.70-0.40+0.45 × 10−11 cm3 s−1. A limit of detection of 4.0 × 10−5, in absorbance terms, can be achieved, which equates to a limit of detection of ∼ 2 × 1011 cm−3 for CH2OO, monitored at 1285.7 cm−1, based on the detection path length of (218 ± 20) cm. Initial results, directly monitoring SO3 at 1388.7 cm−1, demonstrate that SO3 is the reaction product for CH2OO + SO2. The use of mid-IR QCL absorption spectroscopy offers significant advantages over alternative techniques commonly used to determine reaction kinetics, such as laser-induced fluorescence (LIF) or ultraviolet absorption spectroscopy, owing to the greater number of species to which IR measurements can be applied. There are also significant advantages over alternative IR techniques, such as step-scan FT-IR, owing to the coherence and increased intensity and spectral resolution of the QCL source and in terms of cost. The instrument described in this work has potential applications in atmospheric chemistry, astrochemistry, combustion chemistry, and in the monitoring of trace species in industrial processes and medical diagnostics.

Optimization of gain region in mid-IR ( ≈ 5 μm) QCL.

Non-equilibrium Green's function (NEGF) formalism is used to optimize the gain region of a quantum cascade laser (QCL) tailored to emit radiation at ∼5 µm wavelength, originally designed by Evans et al. [Appl. Phys. Lett., 88,051105(2006)10.1063/1.2171476]. The optimization strategy uses electron-photon selfenergies to find characteristics of devices under the "operating conditions," i.e., interacting with the laser field. These conditions can be quite different from the one when the device is in no-lasing state and the unsaturated gain is being optimized. The saturation caused by the optical field can push the structure from strong to weak coupling conditions, what changes laser parameters in a non-linear manner. Moreover, the NEGF method does not require any phenomenological parameters (such as, e.g., the phase relaxation times), so the quantities dependent on these parameters are determined solely on physical grounds. The use of the above procedure for the structure under investigation shows that the increase of the quantum efficiency by 24% and the output power by 83% in comparison to the original design can be achieved when the widths of injection and extraction barriers are changed to their optimal values.

Monolithic, Optically Coupled, Multi-Section Mid-IR Quantum Cascade Lasers

Mid-infrared (mid-IR λ ≈ 3–12 μm), single-mode-emission Quantum Cascade Lasers (QCLs) are of significant interest for a wide range of applications, especially as the laser sources are chosen for laser absorption spectroscopy. In this work, we present the design, fabrication and characterization of multi-section, coupled-cavity, mid-IR quantum cascade lasers. The purpose of this work is to propose a design modification for a coupled-cavity device, yielding a single-mode emission with a longer range of continuous tuning during the pulse, in contrast to a 2-section device. This effect was obtained and demonstrated in the work. The proposed design of a 3-section coupled-cavity QCL allows for a single-mode emission with 35 dB side-mode suppression ratio. Additionally, the time-resolved spectra of the wavelength shift during pulse operation, show a continuous tuning of ~3 cm−1 during the 2 μs pulse. The devices were fabricated in a slightly modified, standard laser process using dry etching.

Octave-spanning low-loss mid-IR waveguides based on semiconductor-loaded plasmonics

Plasmonic waveguides are crucial building blocks for integrated on-chip mid-infrared (mid-IR) sensors, which have recently attracted great interest as a sensing platform to target enhanced molecular sensing. However, while hosting a wide range of applications from spectroscopy to telecommunication, the mid-IR lacks suitable broadband solutions that provide monolithic integration with III-V materials. This work reports a novel concept based on hybrid semiconductor-metal surface plasmon polariton waveguides, which result in experimentally demonstrated low loss and broadband devices. Composed of a thin germanium slab on top of a gold layer, the waveguiding properties can be directly controlled by changing the geometrical parameters. The measured losses of our devices are as low as 6.73 dB/mm at 9.12 µm and remain <15 dB/mm in the mid-IR range of 5.6–11.2 µm. The octave-spanning capability of the waveguides makes them ideal candidates for combination with broadband mid-IR quantum cascade laser frequency combs and integrated spectroscopic sensors.

Application of continuous wave quantum cascade laser in combination with CIVP spectroscopy for investigation of large organic and organometallic ions.

Rapidly developing mid-infrared quantum cascade laser (QCL) technology gives easy access to broadly tunable mid-IR laser radiation at a modest cost. Despite several applications of QCL in the industry, its usage for spectroscopic investigation of synthetically relevant organic compounds has been limited. Here, we report the application of an external cavity, continuous wave, mid-IR QCL to cryogenic ion vibrational predissociation spectroscopy to analyze a set of large organic molecules, organometallic complexes, and isotopically labeled compounds. The obtained spectra of test molecules are characterized by a high signal-to-noise ratio and low full width at half-maximum-values, allowing the assignment of two compounds with just a few wavenumber difference. Data generated by cw-QCL and spectra produced by another standard Nd:YAG difference-frequency generation system are compared and discussed.

Conformational changes of a membrane protein determined by infrared difference spectroscopy beyond the diffraction limit

Optogenetics is a revolutionary method for studying neural activity by exploiting the optical stimulation of neurons made possible by artificial genetic expression of light-sensitive transmembrane ``gate'' proteins. Evidence of functional conformational changes of the gate proteins can be obtained by difference infrared (IR) absorption spectroscopy triggered by light stimuli. Here we investigate the effect on the photocycle of the prototype optogenetic protein channelrhodopsin (ChR2) of gold surfaces placed in close proximity to the protein molecules. In order to do this, we bring difference IR spectroscopy to the nanoscale, using a platform based on the coupling of a tunable mid-IR quantum cascade laser and an atomic force microscope (AFM). Sensitivity to individual subwavelength-sized membrane patches, embedding fewer than a hundred ChR2 molecules, is achieved by taking advantage of a plasmonic field enhancement in the nanogap between the gold-coated AFM tip and an ultraflat gold surface used as a sample support. We obtain relative difference absorption variations smaller than ${10}^{\ensuremath{-}2}$ and benchmark nanospectroscopy difference spectra against those taken with the Fourier transform IR (FTIR) spectroscopic technique on the same sample. We identify distinct simultaneous processes in the ChR2 photocycle by performing singular value decomposition of the FTIR difference spectra, and use this procedure to compare IR nanospectroscopy data on individual membrane patches in contact with gold surfaces with those obtained on thick stacks of membrane patches unexposed to metal surfaces. ChR2 proteins maintain their gate function when placed in a 14-nm-wide gap between two gold surfaces, apart from minor modifications to their kinetics. Our results are relevant to optogenetic applications that require physical contact between nanoscale metallic probes and electrodes and the membrane of single neuronal cells. More generally, our work paves the way towards the spectroscopic study of transmembrane proteins at the nanoscale.

Self-starting harmonic comb emission in THz quantum cascade lasers

Harmonic comb states have proven to be ubiquitous in mid-IR quantum cascade lasers. We report here on robust, pure, self-starting harmonic mode locking in Copper-based double-metal THz quantum cascade lasers. Different harmonic orders can be excited in the same laser cavity depending on the pumping condition, and stable harmonic combs spanning more than 600 GHz at 80 K are reported. Such devices can be RF injected, and the free running coherence is assessed by means of a self-mixing technique performed at 50 GHz. A theoretical model based on Maxwell-Bloch equations including an asymmetry in the gain profile is used to interpret the data.