K. M. Johansen

Deuterium diffusion and trapping in hydrothermally grown single crystalline ZnO

Secondary ion mass spectrometry is employed to investigate diffusion of H2 implanted in hydrothermally grown single crystal ZnO. Diffusion profiles have been studied after 30 min isochronal heat treatments from 100 to 400 °C and evaluated using three different models: the infinite source model, a solid solubility limited model, and a trap limited model. Only the latter one reproduces closely the measured values. From this model an activation energy Ea=0.85 eV is extracted, and it is speculated that trapping may be a source of the discrepancies between the reported values of Ea in the literature.

Diffusion and configuration of Li in ZnO

Diffusion of Li into ZnO from an “infinite” surface source under oxygen-rich conditions is studied using secondary ion mass spectrometry. The Li concentration-versus-depth profiles exhibit a distinct and sharp drop, which evolves in position with temperature and time. The sharp drop is associated with an efficient conversion from highly mobile Li-interstitials (Lii) to practically immobile Li-substitutionals (LiZn) via a kick-out mechanism. The characteristic concentration level at which Li drops provides a measure of the active donor concentration in the samples at the processing temperature, and gives evidence of residual impurities being responsible for the commonly observed “native” n-type conductivity. These donors are suggested to arise from different impurities, with Al and Si as the prevailing ones in hydrothermal and melt grown material. Further, evidence of electric field effects on Li diffusion profiles is obtained, and they are considered as a main reason for the slow diffusivity obtained in t...

Defect segregation and optical emission in ZnO nano- and microwires

The spatial distribution of defect related deep band emission has been studied in zinc oxide (ZnO) nano- and microwires using depth resolved cathodoluminescence spectroscopy (DRCLS) in a hyperspectral imaging (HSI) mode within a UHV scanning electron microscope (SEM). Three sets of wires were examined that had been grown by pulsed laser deposition or vapor transport methods and ranged in diameter from 200 nm-2.7 μm. This data was analyzed by developing a 3D DRCLS simulation and using it to estimate the segregation depth and decay profile of the near surface defects. We observed different dominant defects from each growth process as well as diameter-dependent defect segregation behavior.

Defect formation and thermal stability of H in high dose H implanted ZnO

implantation is found to create deformed layers with a uniaxial strain of 0.5–2.4% along the c-axis in ZnO, for the low and high dose, respectively. About 0.2–0.4% of the original implanted H concentration can still be detected in the samples by secondary ion mass spectrometry after annealing at a temperature up to 800 � C. The thermally stable H is tentatively attributed to H related defect complexes involving the substitutional H that are bound to O vacancies and/or the highly mobile interstitial H that are bound to substitutional Li occupying Zn vacancies as the samples are cooled slowly from high temperature annealing. H implantation to a dose of 1 � 10 17 cm � 2 and followed by annealing at 800 � C, is found to result in the formation of vacancy clusters that evolved into faceted voids with diameter varying from 2 to 30 nm. The truncations around the voids form more favorably on the O-terminated surface than on the Zn-terminated surface, suggesting that O is a preferred surface polarity for the internal facets of the voids in the presence of H. V C 2013 AIP Publishing LLC.

Thermal stability of the OH–Li complex in hydrothermally grown single crystalline ZnO

The thermal stability of the prominent 3577 cm−1 infrared absorption band in ZnO, assigned to an O–H stretch mode adjacent to a Li atom on Zn site (LiZn), is studied. Employing slow sample cooling after annealing, the 3577 cm−1 peak remains at temperatures ≤1250 °C, consistent with previous reports. However, if the samples are cooled rapidly by quenching, the peak disappears after annealing for 1 h at 650 °C. A dissociation energy of less than 2.5 eV is deduced for the OH–LiZn complex and the apparent high thermal stability after slow cooling is attributed to efficient recapturing of H by LiZn. Moreover, deuterium (D) is found to replace hydrogen in OH–LiZn after 1 h at 700 °C in D2 gas.

Zn vacancy as a polaronic hole trap in ZnO

This work explores the Zn vacancy in ZnO using hybrid density functional theory calculations. The Zn vacancy is predicted to be an exceedingly deep polaronic acceptor that can bind a localized hole on each of the four nearest-neighbor O ions. The hole localization is accompanied by a distinct outward relaxation of the O ions, which leads to lower symmetry and reduced formation energy. Notably, we find that initial symmetry-breaking is required to capture this effect, which might explain the absence of polaronic hole localization in some previous hybrid density functional studies. We present a simple model to rationalize our findings with regard to the approximately equidistant thermodynamic charge-state transition levels. Furthermore, by employing a one-dimensional configuration coordinate model with parameters obtained from the hybrid density functional theory calculations, luminescence lineshapes were calculated. The results show that the isolated Zn vacancy is unlikely to be the origin of the commonly observed luminescence in the visible part of the emission spectrum from \textit{n}-type material, but rather the luminescence in the infrared region.

Process dependence of H passivation and doping in H-implanted ZnO

We used depth-resolved cathodoluminescence spectroscopy (DRCLS), photoluminescence (PL) spectroscopy and temperature-dependent Hall-effect (TDHE) measurements to describe the strong dependence of H passivation and doping in H-implanted ZnO on thermal treatment. Increasing H implantation dose increases passivation of Zn and oxygen vacancy-related defects, while reducing deep level emissions. Over annealing temperatures of 100‐400 ◦ Ca t different times, 1h annealing at 200 ◦ C yielded the lowest DRCLS deep level emissions, highest TDHE carrier mobility, and highest near band-edge PL emission. These results describe the systematics of dopant implantation and thermal activation on H incorporation in ZnO and their effects on its electrical properties. (Some figures may appear in colour only in the online journal)

Nanoscale mapping of optical band gaps using monochromated electron energy loss spectroscopy

Using monochromated electron energy loss spectroscopy in a probe-corrected scanning transmission electron microscope we demonstrate band gap mapping in ZnO/ZnCdO thin films with a spatial resolution below 10 nm and spectral precision of 20 meV.

Hydrothermally grown single-crystalline zinc oxide; characterization and modification

An overview of our recent results on characterization and modification of high-resistivity n-type bulk zinc oxide samples, grown by hydrothermal techniques, is given. Three specific topics are addr ...

The temperature-dependency of the optical band gap of ZnO measured by electron energy-loss spectroscopy in a scanning transmission electron microscope

The optical band gap of ZnO has been measured as a function of temperature using Electron Energy-Loss Spectroscopy (EELS) in a (Scanning) Transmission Electron Microscope ((S)TEM) from approximately 100 K up towards 1000 K. The band gap narrowing shows a close to linear dependency for temperatures above 250 K and is accurately described by Varshni, Bose-Einstein, Passler and Manoogian-Woolley models. Additionally, the measured band gap is compared with both optical absorption measurements and photoluminescence data. STEM-EELS is here shown to be a viable technique to measure optical band gaps at elevated temperatures, with an available temperature range up to 1500 K and the benefit of superior spatial resolution.