Anomalous Temperature Effect in Weakly Coupled Superlattices: Carrier Transport in a THz Quantum Cascade Laser.

We present an investigation into the vertical transport through 13 different superlattice structures, where the well and barrier widths, doping concentration, dopant position, and contact layers were varied. Although superlattices have been extensively studied since 1970, there is a lack of publications on transport through superlattices similarly low doped as THz quantum cascade lasers (QCLs), for which the doping is in the 3-5×10^{10} cm^{-2} range. The superlattices presented are doped in the same range as THz QCLs, with contact layers and fabrication comparable to high-temperature THz QCLs. The temperature-dependent current-voltage characteristics were measured starting from 5 K and an anomalous temperature effect was observed at the first plateau. The measured current through the superlattice first decreases before increasing again with increasing temperature, resulting in the lowest current occurring at 75-110 K. This behavior is also observed in some THz QCLs. The effect disappears for thinner barriers, higher quantum well doping, or modified contact layers, indicating a strong dependency on band bending, due to the large difference in the doping of the contact layers and the superlattice, which is confirmed with multiscattering Büttiker simulations.

Beyond Karl Fischer titration: a monolithic quantum cascade sensor for monitoring residual water concentration in solvents.

Quality control of liquids is an important part of analytical chemistry. The gold standard for measuring residual water in organic solvents and pharmaceutical applications is Karl Fischer titration. It has a high sensitivity, selectivity and accuracy. The downsides are a time-consuming offline analysis, together with the need for toxic reagents producing waste, and it suffers from poor inter-laboratory reproducibility. In this work, we present a high-performance lab-on-a-chip sensor exploiting mid-IR spectroscopy for liquid sensing. It is operating at 6.1 µm wavelength and is suitable for robust and flexible real-time in situ analysis of the residual water concentration in isopropyl alcohol. This is demonstrated in two experiments. A custom-made 60 µL flow cell is employed to measure only minute amounts of analyte in an inline configuration. In a second approach, the whole sensor is immersed into the analyte to demonstrate sensitive and rapid in situ operation on the millisecond time scale. This is confirmed by the ability for time resolved single water-droplet monitoring, while they are mixed into the liquid sample. We obtain a limit of detection between 120 ppm and 150 ppm with a concentration coverage spanning three orders of magnitude from 1.2 × 10-2%vol to 25%vol for the flow cell and 1.5 × 10-2%vol to 19%vol in the in situ configuration, respectively.

A mid-infrared lab-on-a-chip for dynamic reaction monitoring.

Mid-infrared spectroscopy is a sensitive and selective technique for probing molecules in the gas or liquid phase. Investigating chemical reactions in bio-medical applications such as drug production is recently gaining particular interest. However, monitoring dynamic processes in liquids is commonly limited to bulky systems and thus requires time-consuming offline analytics. In this work, we show a next-generation, fully-integrated and robust chip-scale sensor for online measurements of molecule dynamics in a liquid solution. Our fingertip-sized device utilizes quantum cascade technology, combining the emitter, sensing section and detector on a single chip. This enables real-time measurements probing only microliter amounts of analyte in an in situ configuration. We demonstrate time-resolved device operation by analyzing temperature-induced conformational changes of the model protein bovine serum albumin in heavy water. Quantitative measurements reveal excellent performance characteristics in terms of sensor linearity, wide coverage of concentrations, extending from 0.075 mg ml-1 to 92 mg ml-1 and a 55-times higher absorbance than state-of-the-art bulky and offline reference systems.

Mesoporous Zirconia Coating for Sensing Applications Using Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Spectroscopy.

Mid-infrared attenuated total reflection (ATR) spectroscopy is a powerful tool for in situ monitoring of various processes. Mesoporous silica, an extensively studied material, has already been applied in sensing schemes due to its high surface area and tunable surface chemistry. However, its poor chemical stability in aqueous solutions at pH values higher than 8 and strong absorption below 1250 cm-1 limits its range of applications. To circumvent these problems, a mesoporous zirconia coating on ATR crystals was developed. Herein, the synthesis, surface modification, and characterization of ordered mesoporous zirconia films on Si wafers and Si-ATR crystals are presented. The modified coating was applied in sensing schemes using aromatic and aliphatic nitriles in aqueous solution as organic pollutants. The mesoporous zirconia coating shows strong chemical resistance when kept in alkaline solution for 72 h. The success of surface modification is confirmed using Fourier transform infrared (FT-IR) spectroscopy and contact angle measurements. Benzonitrile and valeronitrile in water are used as model analytes to evaluate the enrichment performance of the film. The experimental results are fitted using Freundlich isotherms, and enrichment factors of 162 and 26 are calculated for 10 mg L-1 benzonitrile and 25 mg L-1 valeronitrile in water, respectively. Limits of detection of 1 mg L-1 for benzonitrile and 11 mg L-1 for valeronitrile are obtained. The high chemical stability of this coating allows application in diverse fields such as catalysis with the possibility of in situ monitoring using FT-IR spectroscopy.

Deep learning control of THz QCLs.

Artificial neural networks are capable of fitting highly non-linear and complex systems. Such complicated systems can be found everywhere in nature, including the non-linear interaction between optical modes in laser resonators. In this work, we demonstrate artificial neural networks trained to model these complex interactions in the cavity of a Quantum Cascade Random Laser. The neural networks are able to predict modulation schemes for desired laser spectra in real-time. This radically novel approach makes it possible to adapt spectra to individual requirements without the need for lengthy and costly simulation and fabrication iterations.

d-Glucose Adsorption on the TiO2 Anatase (100) Surface: A Direct Comparison Between Cluster-Based and Periodic Approaches.

Titanium dioxide (TiO2) has been extensively studied as a suitable material for a wide range of fields including catalysis and sensing. For example, TiO2-based nanoparticles are active in the catalytic conversion of glucose into value-added chemicals, while the good biocompatibility of titania allows for its application in innovative biosensing devices for glucose detection. A key process for efficient and selective biosensors and catalysts is the interaction and binding mode between the analyte and the sensor/catalyst surface. The relevant features regard both the molecular recognition event and its effects on the nanoparticle electronic structure. In this work, we address both these features by combining two first-principles methods based on periodic boundary conditions and cluster approaches (CAs). While the former allows for the investigation of extended materials and surfaces, CAs focus only on a local region of the surface but allow for using hybrid functionals with low computational cost, leading to a highly accurate description of electronic properties. Moreover, the CA is suitable for the study of reaction mechanisms and charged systems, which can be cumbersome with PBC. Here, a direct and detailed comparison of the two computational methodologies is applied for the investigation of d-glucose on the TiO2 (100) anatase surface. As an alternative to the commonly used PBC calculations, the CA is successfully exploited to characterize the formation of surface and subsurface oxygen vacancies and to determine their decisive role in d-glucose adsorption. The results of such direct comparison allow for the selection of an efficient, finite-size structural model that is suitable for future investigations of biosensor electrocatalytic processes and biomass conversion catalysis.

Cyclic Carbonate Formation from Epoxides and CO2 Catalyzed by Sustainable Alkali Halide-Glycol Complexes: A DFT Study to Elucidate Reaction Mechanism and Catalytic Activity.

We provide a comprehensive DFT investigation of the mechanistic details of CO2 fixation into styrene oxide to form styrene carbonate, catalyzed by potassium iodide-tetraethylene glycol complex. A detailed view on the intermediate steps of the overall reaction clarifies the role of hydroxyl substances as co-catalysts for the alkali halide-catalyzed cycloaddition. The increase of iodide nucleophilicity in presence of tetraethylene glycol is examined and rationalized by NBO and Hirshfeld charge analysis, and bond distances. We explore how different alkali metal salts and glycols affect the catalytic performance. Our results provide important hints on the synthesis of cyclic carbonates from CO2 and epoxides promoted by alkali halides and glycol complexes, allowing the development of more efficient catalysts.

Thermoelectric-cooled terahertz quantum cascade lasers.

We demonstrate the first lasing emission of a thermo-electrically cooled terahertz quantum cascade laser (THz QCL). A high temperature three-well THz QCL emitting at 3.8 THz is mounted to a novel five-stage thermoelectric cooler reaching a temperature difference of ΔT = 124 K. The temperature and time-dependent laser performance is investigated and shows a peak pulse power of 4.4 mW and a peak average output power of 100 µW for steady-state operation.

Suppression of axial growth by boron incorporation in GaAs nanowires grown by self-catalyzed molecular beam epitaxy.

The addition of boron to GaAs nanowires grown by self-catalyzed molecular beam epitaxy was found to have a strong effect on the nanowire morphology, with axial growth greatly reduced as the nominal boron concentration was increased. Transmission electron microscopy measurements show that the Ga catalyst droplet was unintentionally consumed during growth. Concurrent radial growth, a rough surface morphology and tapering of nanowires grown under boron flux suggest that this droplet consumption is due to reduced Ga adatom diffusion on the nanowire sidewalls in the presence of boron. Modelling of the nanowire growth puts the diffusion length of Ga adatoms under boron flux at around 700-1000 nm. Analyses of the nanowire surfaces show regions of high boron concentration, indicating the surfactant nature of boron in GaAs.

Ring quantum cascade lasers with twisted wavefronts.

We demonstrate the on-chip generation of twisted light beams from ring quantum cascade lasers. A monolithic gradient index metamaterial is fabricated directly into the substrate side of the semiconductor chip and induces a twist of the light's wavefront. This significantly influences the obtained beam pattern, which changes from a central intensity minimum to a maximum depending on the discontinuity count of the metamaterial. Our design principle provides an interesting alternative to recent implementations of microlasers operating at an exceptional point.

Barrier Height Tuning of Terahertz Quantum Cascade Lasers for High-Temperature Operation.

Terahertz quantum cascade lasers (QCLs) are excellent coherent light sources, but are still limited to an operating temperature below 200 K. To tackle this, we analyze the influence of the barrier height for the identical three-well terahertz QCL layer sequence by comparing different aluminum concentrations (x = 0.12-0.24) in the GaAs/Al x Ga1-x As material system, and then we present an optimized structure based on these findings. Electron injection and extraction mechanisms as well as LO-phonon depopulation processes play crucial roles in the efficient operation of these lasers and are investigated in this study. Experimental results of the barrier height study show the highest operating temperature of 186.5 K for the structure with 21% aluminum barriers, with a record k B T max/ℏω value of 1.36 for a three-well active region design. An optimized heterostructure with 21% aluminum concentration and reduced cavity waveguide losses is designed and enables a record operating temperature of 196 K for a 3.8 THz QCL.

Room-Temperature Quantum Ballistic Transport in Monolithic Ultrascaled Al-Ge-Al Nanowire Heterostructures.

Conductance quantization at room temperature is a key requirement for the utilizing of ballistic transport for, e.g., high-performance, low-power dissipating transistors operating at the upper limit of "on"-state conductance or multivalued logic gates. So far, studying conductance quantization has been restricted to high-mobility materials at ultralow temperatures and requires sophisticated nanostructure formation techniques and precise lithography for contact formation. Utilizing a thermally induced exchange reaction between single-crystalline Ge nanowires and Al pads, we achieved monolithic Al-Ge-Al NW heterostructures with ultrasmall Ge segments contacted by self-aligned quasi one-dimensional crystalline Al leads. By integration in electrostatically modulated back-gated field-effect transistors, we demonstrate the first experimental observation of room temperature quantum ballistic transport in Ge, favorable for integration in complementary metal-oxide-semiconductor platform technology.

High-Power Growth-Robust InGaAs/InAlAs Terahertz Quantum Cascade Lasers.

We report on high-power terahertz quantum cascade lasers based on low effective electron mass InGaAs/InAlAs semiconductor heterostructures with excellent reproducibility. Growth-related asymmetries in the form of interface roughness and dopant migration play a crucial role in this material system. These bias polarity dependent phenomena are studied using a nominally symmetric active region resulting in a preferential electron transport in the growth direction. A structure based on a three-well optical phonon depletion scheme was optimized for this bias direction. Depending on the sheet doping density, the performance of this structure shows a trade-off between high maximum operating temperature and high output power. While the highest operating temperature of 155 K is observed for a moderate sheet doping density of 2 × 1010 cm-2, the highest peak output power of 151 mW is found for 7.3 × 1010 cm-2. Furthermore, by abutting a hyperhemispherical GaAs lens to a device with the highest doping level a record output power of 587 mW is achieved for double-metal waveguide structures.

Spectrally resolved far-fields of terahertz quantum cascade lasers.

We demonstrate a convenient and fast method to measure the spectrally resolved far-fields of multimode terahertz quantum cascade lasers by combining a microbolometer focal plane array with an FTIR spectrometer. Far-fields of fundamental TM0 and higher lateral order TM1 modes of multimode Fabry-Pérot type lasers have been distinguished, which very well fit to the results obtained by a 3D finite-element simulation. Furthermore, multimode random laser cavities have been investigated, analyzing the contribution of each single laser mode to the total far-field. The presented method is thus an important tool to gain in-depth knowledge of the emission properties of multimode laser cavities at terahertz frequencies, which become increasingly important for future sensing applications.

Remote Sensing with Commutable Monolithic Laser and Detector.

The ubiquitous trend toward miniaturized sensing systems demands novel concepts for compact and versatile spectroscopic tools. Conventional optical sensing setups include a light source, an analyte interaction region, and a separate external detector. We present a compact sensor providing room-temperature operation of monolithic surface-active lasers and detectors integrated on the same chip. The differentiation between emitter and detector is eliminated, which enables mutual commutation. Proof-of-principle gas measurements with a limit of detection below 400 ppm are demonstrated. This concept enables a crucial miniaturization of sensing devices.

Advanced gas sensors based on substrate-integrated hollow waveguides and dual-color ring quantum cascade lasers.

This study shows the first combination of a ring-shaped vertically emitting quantum cascade laser (riQCL) providing two distinct emission wavelengths combined with a substrate-integrated hollow waveguide (iHWG). This ultra-compact riQCL-iHWG gas sensing device enables the simultaneous detection of two vapor phase species - here, furan and 2-methoxyethanol - providing distinctive absorption features at the emission wavelengths of the riQCL (i.e., 1144 and 1170 cm-1). Hence, multianalyte gas sensing via a unique mid-infrared (MIR) sensor concept is demonstrated.

Mid-infrared surface transmitting and detecting quantum cascade device for gas-sensing.

We present a bi-functional surface emitting and surface detecting mid-infrared device applicable for gas-sensing. A distributed feedback ring quantum cascade laser is monolithically integrated with a detector structured from a bi-functional material for same frequency lasing and detection. The emitted single mode radiation is collimated, back reflected by a flat mirror and detected by the detector element of the sensor. The surface operation mode combined with the low divergence emission of the ring quantum cascade laser enables for long analyte interaction regions spatially separated from the sample surface. The device enables for sensing of gaseous analytes which requires a relatively long interaction region. Our design is suitable for 2D array integration with multiple emission and detection frequencies. Proof of principle measurements with isobutane (2-methylpropane) and propane as gaseous analytes were conducted. Detectable concentration values of 0-70% for propane and 0-90% for isobutane were reached at a laser operation wavelength of 6.5 µm utilizing a 10 cm gas cell in double pass configuration.

Measurement of bound states in the continuum by a detector embedded in a photonic crystal.

We directly measure optical bound states in the continuum (BICs) by embedding a photodetector into a photonic crystal slab. The BICs observed in our experiment are the result of accidental phase matching between incident, reflected and in-plane waves at seemingly random wave vectors in the photonic band structure. Our measurements were confirmed through a rigorously coupled-wave analysis simulation in conjunction with temporal coupled mode theory. Polarization mixing between photonic crystal slab modes was observed and described using a plane wave expansion simulation. The ability to probe the field intensity inside the photonic crystal and thereby to directly measure BICs represents a milestone in the development of integrated opto-electronic devices based on BICs.

The influence of whispering gallery modes on the far field of ring lasers.

We introduce ring lasers with continuous π-phase shifts in the second order distributed feedback grating. This configuration facilitates insights into the nature of the modal outcoupling in an optical cavity. The grating exploits the asymmetry of whispering gallery modes and induces a rotation of the far field pattern. We find that this rotation can be connected to the location of the mode relative to the grating. Furthermore, the direction of rotation depends on the radial order of the whispering gallery mode. This enables a distinct identification and characterization of the mode by simple analysis of the emission beam.

Quantum cascade lasers with a tilted facet utilizing the inherent polarization purity.

We report on quantum cascade lasers (QCLs) with a tilted facet utilizing their polarization property. Contrary to diode lasers, QCLs generate purely TM polarized light due to the intersubband selection rules. This property enables the utilization of reflectivity in terms of only TM polarized light (TM reflectivity). The TM reflectivity is reduced by tilting the front facet, resulting in enhanced light output power from the tilted facet. The peak output power of a QCL with a facet angle of 12° are increased by 31 %. The slope efficiency of a QCL with a facet angle of 17° are increased by 43 %. Additionally, a peculiar property of TM reflectivity, the Brewster angle, is investigated by using COMSOL simulations to find its availability in QCLs.