Jan Eric Stehr

Crystalline ZnO with an enhanced surface area obtained by nanocasting

The authors report the synthesis of nanoporous ZnO, which exhibits a periodically ordered, uniform pore system with crystalline pore walls. The crystalline structure is investigated by x-ray diffraction, transmission electron microscopy, and selected area electron diffraction. The large specific surface area and the uniformity of the pore system are confirmed by nitrogen physisorption. Raman spectroscopy along with low-temperature photoluminescence measurements confirms the high degree of crystallinity and gives insight into defects participating in the radiative recombination processes.

Mechanism for radiative recombination and defect properties of GaP/GaNP core/shell nanowires

Recombination processes in GaP/GaNP core/shell nanowires (NWs) grown on a Si substrate by molecular beam epitaxy are examined using a variety of optical characterization techniques, including cw- and time-resolved photoluminescence and optically detected magnetic resonance (ODMR). Superior optical quality of the structures is demonstrated based on the observation of intense emission from a single NW at room temperature. This emission is shown to originate from radiative transitions within N-related localized states. From ODMR, growth of GaP/GaNP NWs is also found to facilitate formation of complex defects containing a P atom at its core that act as centers of competing non-radiative recombination.

Defects in N, O and N, Zn implanted ZnO bulk crystals

Comprehensive characterization of defects formed in bulk ZnO single crystals co-implanted with N and Zn as well as N and O atoms is performed by means of optically detected magnetic resonance (ODMR) complemented by Raman and photoluminescence (PL) spectroscopies. It is shown that in addition to intrinsic defects such as Zn vacancies and Zn interstitials, several N-related defects are formed in the implanted ZnO. The prevailed configuration of the defects is found to depend on the choices of the co-implants and also the chosen annealing ambient. Specifically, co-implantation with O leads to the formation of (i) defects responsible for local vibrational modes at 277, 511, and 581 cm−1; (ii) a N-related acceptor with the binding energy of 160 ± 40 meV that is involved in the donor-acceptor pair emission at 3.23 eV; and (iii) a deep donor and a deep NO acceptor revealed from ODMR. Activation of the latter defects is found to require post-implantation annealing in nitrogen ambient. None of these defects are detected when N is co-implanted with Zn. Under these conditions, the dominant N-induced defects include a deep center responsible for the 3.3128 eV PL line, as well as an acceptor center of unknown origin revealed by ODMR. Formation mechanisms of the studied defects and their role in carrier recombination are discussed.

Efficient nitrogen incorporation in ZnO nanowires

One-dimensional ZnO nanowires (NWs) are a promising materials system for a variety of applications. Utilization of ZnO, however, requires a good understanding and control of material properties that are largely affected by intrinsic defects and contaminants. In this work we provide experimental evidence for unintentional incorporation of nitrogen in ZnO NWs grown by rapid thermal chemical vapor deposition, from electron paramagnetic resonance spectroscopy. The incorporated nitrogen atoms are concluded to mainly reside at oxygen sites (NO). The NO centers are suggested to be located in proximity to the NW surface, based on their reduced optical ionization energy as compared with that in bulk. This implies a lower defect formation energy at the NW surface as compared with its bulk value, consistent with theoretical predictions. The revealed facilitated incorporation of nitrogen in ZnO nanostructures may be advantageous for realizing p-type conducting ZnO via N doping. The awareness of this process can also help to prevent such unintentional doping in structures with desired n-type conductivity.

Electron paramagnetic resonance and photo-electron paramagnetic resonance investigation on the recharging of the substitutional nitrogen acceptor in ZnO

We investigated the substitutional nitrogen center in ZnO single crystals by electron paramagnetic resonance (EPR) and photo-EPR spectroscopy. Aside the three principle hyperfine lines due to the interaction of the N0 (2p5) electron spin with the nitrogen nucleus (I = 1, natural abundance 99.6%), we identify additional satellite lines which arise from ΔmS = ±1 and ΔmI = ±1, ±2 transitions becoming allowed due to quadrupole interaction. The quadrupole coupling constant e2qQ/h is determined to −5.9 MHz with an asymmetry parameter of η = 0.05. These values are somewhat different from those obtained for the nitrogen center in ZnO powders, but are closer to the theoretical calculations of Gallino et al. We further carefully investigated the photon induced recharging of the N centers. We determine the energy hυ required for the process NO− + hυ → NO0 + ecb− to 2.1 ± 0.05 eV, the dependence of the EPR signal intensity on the illumination time shows a mono-exponential behavior which gives evidence that a direct i...

Comparison of the magnetic properties of GaInAs/MnAs and GaAs/MnAs hybrids with random and ordered arrangements of MnAs nanoclusters

Random arrangements of ferromagnetic MnAs nanoclusters were deposited on (111)B-GaInAs surfaces by standard metal-organic vapor-phase epitaxy (MOVPE). Ordered arrangements of MnAs nanoclusters and cluster chains were obtained by selective-area MOVPE on prepatterned (111)B-GaAs substrates. This new method enables one to control the arrangement of nanoclusters in the growth process offering interesting opportunities to tune the properties of individual MnAs clusters as well as the interaction between the carriers in the surrounding semiconductor matrix and the clusters. The magnetic anisotropy of the MnAs clusters was investigated by magnetic force microscopy and ferromagnetic resonance measurements. The in-plane magnetic anisotropy is mainly determined by the interplay of cluster shape and magnetocrystalline anisotropy while the hard magnetic axis of the clusters is perpendicular to the sample plane independent of cluster shape. The magnetotransport measurements demonstrate that the cluster arrangements st...

Optimizing GaNP coaxial nanowires for efficient light emission by controlling formation of surface and interfacial defects.

We report on identification and control of important nonradiative recombination centers in GaNP coaxial nanowires (NWs) grown on Si substrates in an effort to significantly increase light emitting efficiency of these novel nanostructures promising for a wide variety of optoelectronic and photonic applications. A point defect complex, labeled as DD1 and consisting of a P atom with a neighboring partner aligned along a crystallographic ⟨ 111 ⟩ axis, is identified by optically detected magnetic resonance as a dominant nonradiative recombination center that resides mainly on the surface of the NWs and partly at the heterointerfaces. The formation of DD1 is found to be promoted by the presence of nitrogen and can be suppressed by reducing the strain between the core and shell layers, as well as by protecting the optically active shell by an outer passivating shell. Growth modes employed during the NW growth are shown to play a role. On the basis of these results, we identify the GaP/GaN(y)P(1-y)/GaN(x)P(1-x) (x < y) core/shell/shell NW structure, where the GaN(y)P(1-y) inner shell with the highest nitrogen content serves as an active light-emitting layer, as the optimized and promising design for efficient light emitters based on GaNP NWs.

Defect properties of ZnO nanowires revealed from an optically detected magnetic resonance study

Optically detected magnetic resonance (ODMR) complemented by photoluminescence measurements is used to evaluate optical and defect properties of ZnO nanowires (NWs) grown by rapid thermal chemical vapor deposition. By monitoring visible emissions, several grown-in defects are revealed and attributed to Zn vacancies, shallow (but not effective mass) donor and exchange-coupled pairs of Zn vacancies and Zn interstitials. It is also found that the intensity of the donor-related ODMR signals is substantially lower in the NWs compared with that in bulk ZnO. This may indicate that formation of native donors is suppressed in NWs, which is beneficial for achieving p-type conductivity.

Optically detected magnetic resonance studies of point defects in quaternary GaNAsP epilayers grown by vapor phase epitaxy

Defect properties of quaternary GaNAsP/GaP epilayers grown by vapor phase epitaxy (VPE) are studied by photoluminescence and optically detected magnetic resonance techniques. Incorporation of more than 0.6% of nitrogen is found to facilitate formation of several paramagnetic defects which act as competing carrier recombination centers. One of the defects (labeled as Gai-D) is identified as a complex defect that has a Ga interstitial (Gai) atom residing inside a Ga tetrahedron as its core. A comparison of Gai-D with other Gai-related defects known in ternary GaNP and GaNAs alloys suggests that this defect configuration is specific to VPE-grown dilute nitrides.

Nonferromagnetic nanocrystalline ZnO:Co thin films doped with Zn interstitials

ZnCoO thin films were synthesized via a wet chemical route and subsequently annealed in Zn vapor to increase the conductivity by introducing Zn interstitials. All samples show small hysteresis loops close to the detection limit of the magnetometer. Thus the samples were thoroughly investigated to obtain evidence for further ferromagneticlike behavior. Optical and magneto-optical experiments show the crystal field transitions of Co2+ in the near infrared and visible spectral range. At energies above 2.8 eV a charge transfer transition of Co2+ is observed. The results of magnetotransport measurements are explained by the formation of an impurity band situated below the conduction band. No further evidence for ferromagnetism is obtained.