The optical properties of excitonic recombinations in bulk, n-type ZnO are investigated by photoluminescence (PL) and spatially resolved cathodoluminescence (CL) measurements. At liquid helium temperature in undoped crystals the neutral donor bound excitons dominate in the PL spectrum. Two electron satellite transitions (TES) of the donor bound excitons allow to determine the donor binding energies ranging from 46 to 73 meV. These results are in line with the temperature dependent Hall effect measurements. In the as-grown crystals a shallow donor with an activation energy of 30 meV controls the conductivity. Annealing annihilates this shallow donor which has a bound exciton recombination at 3.3628 eV. Correlated by magnetic resonance experiments we attribute this particular donor to hydrogen. The Al, Ga and In donor bound exciton recombinations are identified based on doping and diffusion experiments and using secondary ion mass spectroscopy. We give a special focus on the recombination around 3.333 eV, i.e. about 50 meV below the free exciton transition. From temperature dependent measurements one obtains a small thermal activation energy for the quenching of the luminescence of 10 ± 2 meV despite the large localization energy of 50 meV. Spatially resolved CL measurements show that the 3.333 eV lines are particularly strong at crystal irregularities and occur only at certain spots hence are not homogeneously distributed within the crystal contrary to the bound exciton recombinations. We attribute them to excitons bound to structural defects (Y-line defect) very common in II-VI semiconductors. For the bound exciton lines which seem to be correlated with Li and Na doping we offer a different interpretation. Li and Na do not introduce any shallow acceptor level in ZnO which otherwise should show up in donor -acceptor pair recombinations. Nitrogen creates a shallow acceptor level in ZnO. Donor -acceptor pair recombination with the 165 meV deep N-acceptor is found in nitrogen doped and implanted ZnO samples, respectively. In the best undoped samples excited rotational states of the donor bound excitons can be seen in low temperature PL measurements. At higher temperatures we also see the appearance of the excitons bound to the B-valence band, which are approximately 4.7 meV higher in energy.
The gallium gradient in Cu(In,Ga)Se2 (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe2 and CuGaSe2 were calculated using density functional theory. The migration barrier for the InCu antisite in CuGaSe2 is significantly lower compared with the GaCu antisite in CuInSe2, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.
GaN growth on Si is very attractive for low-cost optoelectronics and high-frequency, high-power electronics. It also opens a route towards an integration with Si electronics. Early attempts to grow GaN on Si suffered from large lattice and thermal mismatch and the strong chemical reactivity of Ga and Si at elevated temperatures. The latter problem can be easily solved using gallium-free seed layers as nitrided AlAs and AlN. The key problem for device structure growth on Si is the thermal mismatch leading to cracks for layer thicknesses above 1 µm. Meanwhile, several concepts for strain engineering exist as patterning, Al(Ga)N/GaN superlattices, and low-temperature (LT) AlN interlayers which enable the growth of device-relevant GaN thicknesses. The high dislocation density in the heteropitaxial films can be reduced by several methods which are based on lateral epitaxial overgrowth using ex-situ masking or patterning and by in-situ methods as masking with monolayer thick SiN. With the latter method in combination with strain engineering by LT-AlN interlayers dislocation densities around 109 cm -2 can be achieved for 2.5 µm thick device structures.
Selective-area epitaxy is used to form three-dimensional (3D) GaN structures providing semipolar crystal facets. On full 2-in. sapphire wafers we demonstrate the realization of excellent semipolar material quality by introducing inverse GaN pyramids. When depositing InGaN quantum wells on such a surface, the specific geometry influences thickness and composition of the films and can be nicely modeled by gas phase diffusion processes. Various investigation methods are used to confirm the drastically reduced piezoelectric polarization on the semipolar planes. Complete electrically driven light-emitting diode test structures emitting in the blue and blue/green spectral regions show reasonable output powers in the milliwatt regime. Finally, first results of the integration of the 3D structures into a conventional laser design are presented
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