ZnO single crystals, epilayers, and nanostructures often exhibit a variety of narrow emission lines in the spectral range between 3.33 and 3.35 eV which are commonly attributed to deeply bound excitons (Y lines). In this work, we present a comprehensive study of the properties of the deeply bound excitons with particular focus on the Y 0 transition at 3.333 eV. The electronic and optical properties of these centers are compared to those of the shallow impurity related exciton binding centers (I lines). In contrast to the shallow donors in ZnO, the deeply bound exciton complexes exhibit a large discrepancy between the thermal activation energy and localization energy of the excitons and cannot be described by an effective mass approach. The different properties between the shallow and deeply bound excitons are also reflected by an exceptionally small coupling of the deep centers to the lattice phonons and a small splitting between their two electron satellite transitions. Based on a multitude of different experimental results including magnetophotoluminescence, magnetoabsorption, excitation spectroscopy (PLE), time resolved photoluminescence (TRPL), and uniaxial pressure measurements, a qualitative defect model is developed which explains all Y lines as radiative recombinations of excitons bound to extended structural defect complexes. These defect complexes introduce additional donor states in ZnO. Furthermore, the spatially localized character of the defect centers is visualized in contrast to the homogeneous distribution of shallow impurity centers by monochromatic cathodoluminescence imaging. A possible relation between the defect bound excitons and the green luminescence band in ZnO is discussed. The optical properties of the defect transitions are compared to similar luminescence lines related to defect and dislocation bound excitons in other II-VI and III-V semiconductors.
The chemical reaction of imine groups with vapors of trifluoroacetic anhydride (TFAA) was investigated in detail with X‐ray photoelectron spectroscopy (XPS) for the potential application in chemical derivatization (CD) studies of plasma treated surfaces. Imine groups were at first prepared by converting surface amine groups of a polymer precursor using a common vapor phase derivatization reaction with fluorine tagged aldehydes and ketones. The originally low yield for the imine forming reaction of approx. 50%, performed under standard conditions was dramatically enhanced up to 100% by an own developed procedure using a catalyst. This step allowed to obtain a consistent quantification and interpretation of the complex surface reaction products from different types of imine groups derivatized by TFAA.
The symmetry ordering of the valence bands in ZnO is derived from high-resolution magneto-optical measurements of bound excitons. We report on the experimental observation of a hole state related fine splitting for bound excitons in the Voigt configuration. This splitting is related to a nonzero Landé g value g Ќ for hole states from the A valence band. Based on theoretical considerations, the symmetry of the uppermost valence band is doubtlessly identified as ⌫ 7 . This attribution is confirmed by polarization and angular resolved magnetophotoluminescence spectroscopy.
The main emission characteristics of electrically-driven polariton lasers based on planar GaN microcavities with embedded InGaN quantum wells are studied theoretically. The polariton emission dependence on pump current density is first modeled using a set of semi-classical Boltzmann equations for the exciton-polaritons that are coupled to the rate equation describing the electron-hole plasma population. Two experimentally relevant pumping geometries are considered, namely the direct injection of electrons and holes into the strongly coupled microcavity region and intracavity optical pumping via an embedded light-emitting diode. The theoretical framework allows the determination of the minimum threshold current density J thr,min as a function of lattice temperature and exciton-cavity photon detuning for the two pumping schemes. A J thr,min value of 5 Acm −2 and 6 Acm −2 is derived for the direct injection scheme and for the intracavity optical pumping one, respectively, at room temperature at the optimum detuning. Then an approximate quasi-analytical model is introduced to derive solutions for both the steady-state and high-speed current modulation. This analysis makes it possible to show that the exciton population, which acts as a reservoir for the stimulated relaxation process, gets clamped once the condensation threshold is crossed, a behavior analogous to what happens in conventional laser diodes with the carrier density above threshold. Finally the modulation transfer function is calculated for both pumping geometries and the corresponding cutoff frequency is determined.
The complex dielectric tensor of ZnO in the regime of the excitonic transitions is determined with ellipsometry and analyzed concerning the quantization of the electromagnetic field in terms of coupled polariton-eigenmodes. Negative sections in the real part indicate the significant formation of polaritons for the dipole-allowed excitons of the three upper valence-bands Γ7,Γ9,Γ7. The transverse-longitudinal splittings which separate the upper polariton branch from the lower branch, corresponding to the k-vector of the used light, are deduced precisely for each subband. Mainly for E∥c, additional absorption peaks are observed at the longitudinal B-exciton and closely above. One is considered to be a mixed-mode and the other is seen as a consequence of interference effects in an exciton free surface layer which is also visible in reflectance anisotropy spectroscopy.
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