Mid-infrared Laser Research Articles

Novel zinc-doped carbon nitride (Zn:C3N4) modulated short-pulsed Er:YAP laser in the mid-infrared region

Compared with traditional inorganic semiconductor, organic semiconductor can be flexibly specified by hydrogen bonds, coordination bonds, covalent bonds or ionic bonds, and different molecular frameworks, and thus possess broad application prospects. In order to increase the surface defect content, the Zn ions are further doped. These surface defects tend to catch electrons. The surface state energy level is constituted by surface defects, and supposed to locate between the valence band and the conduction band. The zinc doped carbon nitride (Zn:C3N4) nanofilms, known as an organic semiconductor material, have exhibited many excellent chemical properties and have a very wide application prospect. Herein, the Zn:C3N4 nanofilms are synthesized by the thermal polymerization, and their morphology, structure, and chemical composition are also systemically analyzed. Moreover, We demonstrate a 3 μm Q-switched Er:YAP crystal laser modulated by the Zn:C3N4 saturable absorber. The obtained Q-switching pulses have a shortest pulse width of 162.5 ns and a peak power of 16.5 W at a repetition rate of 192.9 kHz. These results reveal that Zn:C3N4 can be used as the promising nonlinear saturable absorber material in the mid-infrared pulsed lasers.

Peak-power of 25 W passively Q-switched [formula omitted]2.8 [formula omitted]m Er:YAP bulk laser based on a reflective TaSe2 saturable absorber mirror

Improving the overall performance of saturable absorber mirrors (SAMs) based on Two-dimensional (2D) narrow-band-gap materials is critically important in their applications of mid-infrared pulse laser sources. Herein, a reflective TaSe2 SAM with laser-induced damage threshold of ∼12 MW/cm2 was successfully fabricated, the saturable absorption properties around 2.8 μm were characterized with a modulation depth of 5.3% and a total unsaturated loss of 2.2%. With the as-prepared SAM, high-peak-power passively Q-switched Er:YAP laser operation at ∼2.8 μm was realized. For the condition of the maximum absorbed pump power of 8.0 W, the maximum average output power of 0.7 W was obtained with a pulse width of 264 ns at a repetition rate of 105.5 kHz, which corresponds to a maximum single pulse energy of 6.6 μ J and a peak power of 25.1 W.

Ppb-level NH3 photoacoustic sensor combining a hammer-shaped tuning fork and a 9.55 µm quantum cascade laser

We present a quartz enhanced photoacoustic spectroscopy (QEPAS) gas sensor designed for precise monitoring of ammonia (NH3) at ppb-level concentrations. The sensor is based on a novel custom quartz tuning fork (QTF) with a mid-infrared quantum cascade laser emitting at 9.55 µm. The custom QTF with a hammer-shaped prong geometry which is also modified by surface grooves is designed as the acoustic transducer, providing a low resonance frequency of 9.5 kHz and a high-quality factor of 10263 at atmospheric pressure. In addition, a temperature of 50 °C and a large gas flow rate of 260 standard cubic centimeters per minute (sccm) are applied to mitigate the adsorption and desorption effect arising from the polarized molecular of NH3. With 80-mW optical power and 300-ms lock-in integration time, the detection limit is achieved to be 2.2 ppb which is the best value reported in the literature so far for NH3 QEPAS sensors, corresponding to a normalized noise equivalent absorption coefficient of 1.4 × 10−8 W cm−1 Hz−1/2. A five-day continuous monitoring for atmospheric NH3 is performed, verifying the stability and robustness of the presented QEPAS-based NH3 sensor.

Development of interference-free rotational and vibrational thermometry for studies on shock-heated thermochemical non-equilibrium CO

A mid-infrared interference-free laser absorption technique for simultaneously measuring rotational temperature, vibrational temperature, and CO concentration was developed for application to shock-tube studies on thermochemical non-equilibrium CO over 1000–3000 K. Three transition lines in the fundamental vibrational band of CO (P(0, 21), near 4.87 μm, P(1, 21), near 4.93 μm, and P(0, 37), near 5.05 μm) were selected. The P(0, 21)/P(1, 21) line pair was used for vibrational temperature measurements whereas the P(0, 21)/P(0, 37) line pair was used for rotational temperature measurements. Spectroscopic parameters for developing the technique were measured: line strengths and collisional broadening data in Ar were obtained at 1040–2940 K. Validation experiments for the thermometry system were performed in shock-heated thermal-equilibrium CO/Ar mixtures at 1050–3010 K and 1.1–2.8 bar. The time-dependent rotational and vibrational temperatures were measured during the vibrational relaxation processes of CO. The technique showed high sensitivity in detecting the rotational and vibrational temperatures. The measured rotational temperature agreed well with the temperature calculated using the measured pressure and isentropic relationship. The measured vibrational temperature showed good agreement with the predictions using the Landau and Teller theory and Millikan and White relationship. The time-dependent CO concentration during the oxidation processes of n-heptane over a wide temperature range (1350–2750 K) was measured considering n-heptane as one of the alternative fuels for the scramjet. The interference-free laser absorption strategy showed good flexibility in detecting the CO concentration at ultra-high temperatures. The measured results showed overall good agreement with the predictions from two detailed mechanisms and one skeletal mechanism. The reactivity of n-heptane was found to be insensitive to the temperature increase at ultra-high temperatures (>2100 K).

Dissociation process of polyalanine aggregates by free electron laser irradiation.

Polyalanine (polyA) disease-causative proteins with an expansion of alanine repeats can be aggregated. Although curative treatments for polyA diseases have not been explored, the dissociation of polyA aggregates likely reduces the cytotoxicity of polyA. Mid-infrared free electron laser (FEL) successfully dissociated multiple aggregates. However, whether the FEL dissociates polyA aggregates like other aggregates has not been tested. Here, we show that FEL at 6.1 μm experimentally weakened the extent of aggregation of a peptide with 13 alanine repeats (13A), and the irradiated 13A exerted lesser cytotoxicity to neuron-like cells than non-irradiated 13A. Then, we applied molecular dynamics (MD) simulation to follow the dissociation process by FEL. We successfully observed how the intermolecular β-sheet of polyA aggregates was dissociated and separated into monomers with helix structures upon FEL irradiation. After the dissociation by FEL, water molecules inhibited the reformation of polyA aggregates. We recently verified the same dissociation process using FEL-treated amyloid-β aggregates. Thus, a common mechanism underlies the dissociation of different protein aggregates that cause different diseases, polyA disease and Alzheimer's disease. However, MD simulation indicated that polyA aggregates are less easily dissociated than amyloid-β aggregates and require longer laser irradiation due to hydrophobic alanine repeats.

Photonic molecule based on coupled ring quantum cascade lasers

Photonic molecules—particular systems composed of coupled optical resonators—emulate the behavior of complex physical systems exhibiting discrete energy levels. In this work, we present a photonic molecule composed of two strongly coupled, mid-infrared ring quantum cascade lasers. We explore both experimentally and numerically the key features of the photonic molecule such as the energy level splitting of bonding and antibonding supermodes. Due to the large size of the resonators, the energy splitting results in bands containing tens of modes. Each of these modes is furthermore doubly degenerate with respect to the direction of propagation, namely, clockwise and counterclockwise. We explore several methods to carefully break these symmetries of the system in a controlled manner by introducing spatial and temporal asymmetries in the pumping scheme of the ring lasers. By employing these techniques, we achieve a high degree of precision in the dynamic control of the photonic molecule. Owing to their inherent suitability for on-chip integration, this class of devices may enable applications as varied as mid-infrared sensors or a rich playground for studying non-Hermitian photonics and quantum optics with quantum cascade lasers.

Adding a second AgGaS2 stage to Ti:sapphire/BBO/AgGaS2 setups increases mid-infrared power twofold.

We present a method for increasing the power of mid-infrared laser pulses generated by a conventional beta-barium borate (BBO) optical parametric amplifier (OPA) and AgGaS2 difference frequency generation (DFG) pumped by a Ti:sapphire amplifier. The method involves an additional stage of parametric amplification with a second AgGaS2 crystal pumped by selected outputs of the conventional DFG stage. This method does not require additional pump power from the Ti:sapphire laser source and improves the overall photon conversion efficiency for generating mid-infrared light. It merely requires an additional AgGaS2 crystal and dichroic mirrors. Following difference frequency generation, the method reuses near-infrared light (∼1.9 µm), typically discarded, to pump the additional AgGaS2 stage and amplifies the mid-infrared light twofold. We demonstrate and characterize the power, spectrum, duration, and noise of the mid-IR pulses before and after the second AgGaS2 stage. We observe small changes in center frequencies, bandwidth, and pulse duration for ∼150-fs pulses between 4 and 5 µm.

Over 50 W all-fiber mid-infrared supercontinuum laser.

Broadband supercontinuum laser sources in the mid-infrared region have attracted enormous interest and found significant applications in spectroscopy, imaging, sensing, defense, and security. Despite recent advances in mid-infrared supercontinuum laser sources using infrared fibers, the average power of those laser sources is limited to 10-watt-level, and further power scaling to over 50 W (or hundred-watt-level) remains a significant technological challenge. Here, we report an over 50 W all-fiber mid-infrared supercontinuum laser source with a spectral range from 1220 to 3740 nm, by using low loss (<0.1 dB/m) fluorotellurite fibers we developed as the nonlinear medium and a tilted fusion splicing method for reducing the reflection from the fluorotellurite-silica fiber joint. Furthermore, the scalability of all-fiber mid-infrared supercontinuum laser sources using fluorotellurite fibers is analyzed by considering thermal effects and optical damage, which verifies its potential of power scaling to hundred-watt-level. Our results pave the way for realizing all-fiber hundred-watt-level mid-infrared lasers for real applications.

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.

Phase-matching in terahertz quantum cascade laser sources based on Cherenkov difference-frequency mixing

Terahertz quantum cascade laser sources based on intra-cavity Cherenkov difference-frequency generation in dual-wavelength mid-infrared quantum cascade lasers are currently the only monolithic semiconductor laser technology that can deliver continuous-wave coherent terahertz output at room temperature. Because the Cherenkov difference-frequency generation process enables terahertz radiation generation and extraction across a wide range of frequencies, it is often assumed that phase-matching conditions for this process are automatically fulfilled. We theoretically analyze and experimentally demonstrate that phase-matching plays an important role in these devices, and significant improvements in terahertz power output can be achieved by adjusting the waveguide configuration of the quantum cascade lasers to provide better phase-matching.

Single-Mode Segmented Cladding Chalcogenide Glass Fiber With Ultra-Large Mode Area

Small core size in conventional single mode step-indexed chalcogenide fiber could reduce the ability of mid-infrared (mid-IR) laser power delivery due to its limitation of power density. An effective way to solve the problem is to increase mode area with large core size, but this may degrade the beam quality. In this work, a novel mid-IR segmented cladding fiber (SCF) with leakage structure based on chalcogenide glasses was proposed to obtain large mode area, as well as single-mode condition. The leakage loss and effective mode area of the SCF was analyzed by optimizing the segment number <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">N</i> , duty cycle γ and core radius <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">r</i> . The results show that, when <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">N</i> =4, γ=75% and <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">r</i> =33 μm, the mode area is more than 2000 μm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> in the wavelength range of 3-10 μm and the loss ratio of high order modes (LP <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">11</sub> ) to fundamental mode (LP <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">01</sub> ) is more than 300, indicating the SCF can achieve single-mode operation with a large core. Then, a mid-IR SCF was fabricated via an extrude-and-stack technique based on chalcogenide glasses for the first time. The minimum fiber loss is 3.1 dB/m at 8.6 μm, the bend loss is 3 dB when bend radius is 6 mm. Compared with that in the traditional step-index single-mode fiber, it was found that, the mode area in SCF can be increased over 15 times. All these results demonstrate the SCF possesses the potential of high-power mid-IR laser transmission.

Weldability improvement of immiscible polycarbonate/GFRP by femtosecond laser surface treatment

Poor miscibility is an important reason for the non-weldable performance of most dissimilar polymers and their composites, and traditional surface treatments cannot effectively improve the weldability of dissimilar polymers. Therefore, the non-weldability of dissimilar polymers is one of the important factors that limit the application of polymers and their composites. We proposed a surface modification scheme of laser ablation or etching to improve the weldability of immiscible polymers effectively. Experimental studies on femtosecond ultraviolet (UV) laser ablation/etching, mid-infrared laser transmission welding (LTW), and related characterization and mechanical tests were carried out. The experimental results showed that laser ablation induced the deposition of abundant polar oxygen-containing groups on the surface of polycarbonate (PC), which improved the miscibility of PC and polyamide 66 with a glass fibre volume ratio of 30% (PA66GF30) and reduced the weak boundary layer (WBL), thereby improving their chemical bonding performance. Using the compatibilization mechanism induced by laser ablation, the bonding strength of the PC/PA66GF30 joint obtained by LTW was 13.7 MPa, which was much higher than that of the untreated joint (1.4 MPa). However, the grooves generated by laser etching could induce macro-anchoring effect of the hybrid joint. Based on the compatibilization mechanism and macro-anchoring effect, with the selection of appropriate welding power and etching parameters, the bonding strength of the PC/PA66GF30 joint was further increased to 29.7 MPa. This work has demonstrated the feasibility of laser surface treatment (especially etching) to significantly improve the welding strength of immiscible polymers and their composites.

Analytical Method Development Using Quantum Laser Cascade Spectroscopy with Diffuse and Attenuated Total Reflectance for Determining Low Concentrations of Active Pharmaceutical Ingredients

Quantum Cascade Laser Spectroscopy (QCLS) will quantify acetaminophen as an active pharmaceutical ingredient in different low concentrations formulations in tablet presentation. Tablets contain acetaminophen in nine blends ranging from 0.0% to 3.0% w/w, with mannitol, croscarmellose, cellulose, and magnesium stearate, as excipients. The tablets were analyzed in non-contact mode by mid-infrared attenuated total reflectance and diffuse reflectance backscattering. Measurements were conducted covering the spectral range 770–1890 cm-1. Calibrations were generated by applying multivariate analysis using principal component analysis. The high power of the quantum cascade laser-based spectroscopic system attached to attenuated total reflectance and diffuse reflectance backscattering resulted in the design of discrimination methodologies for pharmaceutical applications with acetaminophen as an active pharmaceutical ingredient in the formulation. The main conclusion is that attenuated total reflectance is better for other analyses. For tablet analysis using mid-infrared quantum cascade lasers, diffuse reflectance backscattering is more accurate for predicting the API content. QCLS is gaining even more acceptance as a valuable tool in Process Analytical Technology.

Mid-infrared absorption spectroscopy measurements and model improvements during the oxidation of ammonia/ethanol and ammonia/diethyl ether blends in a shock tube

Blending ammonia with highly active fuels (hydrogen, hydrocarbons, oxygenated hydrocarbons, etc.) has been identified as an efficient way to improve the mixture's reactivity. In this study, the temperature, CO, CO2, H2O, NH3, and NO time-histories were measured simultaneously during the oxidation of ammonia/ethanol and ammonia/diethyl ether (DEE) blends (equivalence ratio ϕ ∼ 1.2) using mid-infrared laser absorption spectroscopy behind reflected shock waves. Various models (ten for ammonia/ethanol and three for ammonia/DEE) were selected to perform the simulation and compared with the measurements. The predictions are very different for both mixtures, among which the CRECK model was selected to perform discussion and kinetics analyses for the ammonia/ethanol mixture and the Shrestha 2022 model was selected for the ammonia/DEE mixture. The CRECK model performs well in predicting the temperature rise/plateau, H2O formation rate/plateau, CO consumption rate/plateau, and CO2 formation rate. However, it underpredicts the CO formation rate and slightly overpredicts the CO2 plateau and NH3 consumption rate; for the NO time-history, the CRECK model well captures the rapid NO formation but underpredicts the near-equilibrium NO concentration and gives an unnormal initial NO production. The Shrestha 2022 model accurately predicts the plateaus of temperature and H2O, but significantly underpredicts the reactivity of the ammonia/DEE mixture and overpredicts the near-equilibrium NO concentration. According to the kinetics analyses, key reactions affecting the species' time-histories were selected. Fourteen reactions in the CRECK model and eight reactions in the Shrestha 2022 model were updated by the reported data or estimations to improve the predictions. However, discrepancies still exist, which are mainly located in the CO formation and NH3 consumption rates. Further effort should mainly focus on these two aspects, as well as the interactions between oxygenated hydrocarbons and ammonia at high temperatures.

Wavelength Dependence of Atomic Excitation for Ar Subject to Intense Midinfrared Laser Pulses

We report experimental and theoretical investigations of wavelength dependence of Rydberg state excitation (RSE) process of Ar subject to intense laser fields. By simultaneously measuring ionization and RSE yields of Ar atoms subject to strong laser fields at a series of wavelengths, we obtain the wavelength scaling law of the ratio of Ar* over Ar+ with respect to the laser intensity, and this result can be well reproduced by a nonadiabatic model, but not by the classical-trajectory Monte Carlo model. Our results indicate that the nonadiabatic corrections of the photoelectron tunneling exit and tunneling probability play a significant role at shorter wavelengths. Analysis shows that the wavelength dependence phenomenon is due to the interplay of the nonadiabatic effect, wave-packet diffusion and Coulomb focusing effect of the liberated electron.

A Mid-Infrared Multifunctional Optical Device Based on Fiber Integrated Metasurfaces.

A metasurface is a two-dimensional structure with a subwavelength thickness that can be used to control electromagnetic waves. The integration of optical fibers and metasurfaces has received much attention in recent years. This integrated device has high flexibility and versatility. We propose an optical device based on fiber-integrated metasurfaces in the mid-infrared, which uses a hollow core anti-resonant fiber (HC-ARF) to confine light transmission in an air core. The integrated bilayer metasurfaces at the fiber end face can achieve transmissive modulation of the optical field emitted from the HC-ARF, and the Fano resonance excited by the metasurface can also be used to achieve refractive index (RI) sensing with high sensitivity and high figure of merit (FOM) in the mid-infrared band. In addition, we introduce a polydimethylsiloxane (PDMS) layer between the two metasurfaces; thus, we can achieve tunable function through temperature. This provides an integrated fiber multifunctional optical device in the mid-infrared band, which is expected to play an important role in the fields of high-power mid-infrared lasers, mid-infrared laser biomedicine, and gas trace detection.

Mid-infrared Laser Spectroscopy of Jet-Cooled Formic Acid Trimer: Mode-Dependent Line Broadening in the C-O Stretching Region.

Building on recent progress in the vibrational spectroscopy of the formic acid trimer, we present the first high-resolution measurements of the jet-cooled laser absorption spectrum of (HCOOH)3. The spectra of the lowest- and highest-frequency C-O stretching fundamentals are analyzed whereas the third band is not observed, complicated by monomer and dimer absorptions at 1219 cm-1 (8.2 μm). Vibration-rotation parameters are obtained for the band at 1172.31512(68) cm-1 whereas the C-O stretch at 1246.33(5) cm-1 exhibits a significantly larger breadth, allowing only resolution of the coarse PQR structure. Vibrational predissociation can be ruled out, and intramolecular vibrational redistribution mechanisms are discussed, particularly coupling to the concerted proton exchange within the cyclic dimer subunit. Ultimately, the question remains open. The prospects of high-resolution measurements of other trimer bands or isotope substitution experiments, which might assist in revealing the mode-specificity of the underlying broadening mechanisms, are discussed.

2637.5 nm Mid-infrared SrWO4 Raman laser intracavity-pumped by an actively Q-switched Ho:YAG laser

We first report a 2.6 µm mid-infrared SrWO4 Raman laser, intracavity-pumped by an actively Q-switched Ho:YAG laser. The 2122 nm fundamental laser was generated from the Ho:YAG laser, which was resonantly pumped by a 1908 nm continuous wave Tm:YLF laser. Based on the stimulated Raman scattering effect of SrWO4 crystal, the fundamental wavelength of 2122 nm was converted into the Raman wavelength of 2637.5 nm, corresponding to the Raman shift of 921 cm−1. The output characteristics of SrWO4 Raman laser were investigated at various repetition frequencies. The maximum average output power was 720 mW at the 6.6 W absorbed pump power and 4 kHz repetition frequency. The maximum single pulse energy and peak power were 196 μJ and 10.9 kW at the 5.6 W absorbed pump power and 3 kHz repetition frequency, respectively. The pulse Raman laser near 2.6 µm has potential applications in material processing, spectroscopy, remote sensing, and nonlinear frequency conversion.

A simplified mid-infrared anti-resonant chalcogenide fiber with fewest resonant peaks.

High-power laser delivery in the mid-infrared via hollow-core fibers is attractive, but it is too difficult to be fabricated using chalcogenide glasses. Here, we designed a mid-infrared hollow-core anti-resonant chalcogenide fiber (HC-ARCF) with a simplified Kagome cladding micro-structure for the first time. Then, the fiber was firstly fabricated through a precision mechanical drilling and pressured fiber drawing method. Ultra-thin walls of 2μm in the fiber lead to the fewest resonance peaks in the 2-5μm among all reported HC-ARCFs. All the fundamental mode, the second-order mode, tube mode and node mode in the fiber were excited and observed at 1550 nm. The power and spectral properties of the core and cladding of HC-ARCF are studied for the first time. The fiber can deliver high-power of 4.84 W without damage with core-coupling, while the threshold of the node in the cladding is only 3.5 W. A broadening of the output spectrum from 1.96 to 2.41μm due to the high nonlinearity at the node was successfully observed under short-pulse laser pumping at 2μm. The potentials of the fiber used for mid-infrared high-power laser delivery via core, or nonlinear laser generation via node, were thus demonstrated.

Low-frequency regular pulse and intermittent oscillation in a mid-infrared interband cascade laser with optoelectronic feedback.

In this work, we experimentally investigate the nonlinear dynamics of a mid-infrared interband cascade laser (ICL) subject to optoelectronic feedback (OEF) through inspecting the time series and power spectrum of the laser output. The results show that, within the range of feedback strength limited by the experiment condition, the ICL sequentially presents stable state, continuously periodical oscillation (CPO), low-frequency regular pulse (LF-RP) and intermittent oscillation state with the increase of feedback strength. For the LF-RP state, the peak-to-peak value and the oscillation period increase with the increase of feedback strength. For the intermittent oscillation state, the time series is composed of the laminar region and burst region appeared alternately, and the average value and standard deviation for the duration of burst region gradually decrease with the increase of feedback strength.