In addition to the nucleophile and solvent, the leaving group has a significant influence on SN2 nucleophilic substitution reactions. Its role is frequently discussed with respect to reactivity, but its influence on the reaction dynamics remains unclear. Here, we uncover the influence of the leaving group on the gas-phase dynamics of SN2 reactions in a combined approach of crossed-beam imaging and dynamics simulations. We have studied the reaction F(-) + CH3Cl and compared it to F(-) + CH3I. For the two leaving groups, Cl and I, we find very similar structures and energetics, but the dynamics show qualitatively different features. Simple scaling of the leaving group mass does not explain these differences. Instead, the relevant impact parameters for the reaction mechanisms are found to be crucial and the differences are attributed to the relative orientation of the approaching reactants. This effect occurs on short timescales and may also prevail in solution-phase conditions.

The proton transfer reaction H3+ + CO is one of the cornerstone chemical processes in the interstellar medium. Here, the dynamics of this reaction have been investigated using crossed beam velocity map imaging. Formyl product cations are found to be predominantly scattered into the forward direction irrespective of the collision energy. In this process, a high amount of energy is transferred to internal product excitation. By fitting a sum of two distribution functions to the measured internal energy distributions, the product isomer ratio is extracted. A small HOC+ fraction is obtained at a collision energy of 1.8 eV, characterized by an upper limit of 24% with a confidence level of 84%. At lower collision energies, the data indicate purely HCO+ formation. Such low values are unexpected given the previously predicted efficient formation of both HCO+ and HOC+ isomers for thermal conditions. This is discussed in light of the direct reaction dynamics that are observed.

We demonstrate terahertz lasing emission from a quantum cascade structure, realized with InAs/AlAs0.16Sb0.84 heterostructures. Due to the lower effective electron mass, InAs based active regions are expected to provide a higher optical gain compared to structures consisting of GaAs or InGaAs. The growth by molecular beam epitaxy enabled the fabrication of monolayer-thick barriers, required for the active region, which is based on a 3-well resonant phonon depletion design. Devices were processed in a double-metal waveguide geometry to ensure high mode confinement and low optical losses. Lasing emission at 3.8 THz was observed at liquid helium temperatures by applying a magnetic field perpendicular to the layered structure in order to suppress parasitic scattering channels. These results demonstrate the feasibility of InAs based active regions for terahertz quantum cascade lasers, potentially enabling higher operating temperatures.

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/AlxGa1-xAs 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 kBTmax/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.

No abstract

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.

Ring resonators are an interesting alternative cavity solution to the commonly used ridge-type waveguide for terahertz (THz) quantum cascade lasers. They either support a standing-wave pattern showing spatial hole burning if there are defects implemented or a traveling mode in a defect-free cavity. Here, we report on ring-shaped THz quantum cascade lasers emitting between 3.2 and 4.1 THz operating in four different emission regimes. The presence of defects in the cavities force the THz quantum cascade laser into a standing-wave pattern. The measurements show a complex behavior highlighting the effect of strong confinement and the optical nonlinearities leading to the generation of a harmonic state, as well as to a fundamental comb, exhibiting over 30 equidistant modes and covering a bandwidth of 622 GHz. The results are explained by numerical calculations based on the Maxwell–Bloch formalism, including the linewidth enhancement factor and reflection points. The compact geometry and high output power (4 mW detected) make these devices extremely appealing for on-chip frequency comb applications in the terahertz region.

We demonstrate UV contact-lithographically fabricated III-V field effect transistors examined over a bandwidth of 100 GHz to 11.8 THz. The zero-bias device reaches a noise equivalent power as low as 250 pW/ √ Hz at 0.6 THz which then increases as f 4 at higher frequencies. The responsivity is modeled by a simple equivalent circuit, showing good agreement over the frequency range of 2 decades. The FETs have been characterized using a photomixer, a quantum cascade laser and a free electron laser, proofing the versatility and large applicability of the detection concept.