Chemical deposition of Cu2O films with ultra-low resistivity: correlation with the defect landscape.

Cuprous oxide (Cu2O) is a promising p-type semiconductor material for many applications. So far, the lowest resistivity values are obtained for films deposited by physical methods and/or at high temperatures (~1000 °C), limiting their mass integration. Here, Cu2O thin films with ultra-low resistivity values of 0.4 Ω.cm were deposited at only 260 °C by atmospheric pressure spatial atomic layer deposition, a scalable chemical approach. The carrier concentration (7.1014-2.1018 cm-3), mobility (1-86 cm2/V.s), and optical bandgap (2.2-2.48 eV) are easily tuned by adjusting the fraction of oxygen used during deposition. The properties of the films are correlated to the defect landscape, as revealed by a combination of techniques (positron annihilation spectroscopy (PAS), Raman spectroscopy and photoluminescence). Our results reveal the existence of large complex defects and the decrease of the overall defect concentration in the films with increasing oxygen fraction used during deposition.

Effects of the pH on the Formation and Doping Mechanisms of ZnO Nanowires Using Aluminum Nitrate and Ammonia.

The elucidation of the fundamental processes in aqueous solution during the chemical bath deposition of ZnO nanowires (NWs) using zinc nitrate and hexamethylenetetramine is of great significance: however, their extrinsic doping by foreign elements for monitoring their optical and electrical properties is still challenging. By combining thermodynamic simulations yielding theoretical solubility plots and speciation diagrams with in situ pH measurements and structural, chemical, and optical analyses, we report an in-depth understanding of the pH effects on the formation and aluminum doping mechanisms of ZnO NWs. By the addition of aluminum nitrate with a given relative concentration for the doping and of ammonia over a broad range of concentrations, the pH is shown to strongly influence the shape, diameter, length, and doping magnitude of ZnO NWs. Tuning the dimensions of ZnO NWs by inhibition of their radial growth only proceeds over a specific pH range, where negatively charged Al(OH)4- complexes are predominantly formed and act as capping agents by electrostatically interacting with the positively charged m-plane sidewalls. These complexes further favor the aluminum incorporation and doping of ZnO NWs, which only operate over the same pH range following thermal annealing above 200 °C. These findings reporting a full chemical synthesis diagram reveal the significance of carefully selecting and following the pH to control the morphology of ZnO NWs as well as to achieve their thermally activated extrinsic doping, as required for many nanoscale engineering devices.

Physical properties of annealed ZnO nanowire/CuSCN heterojunctions for self-powered UV photodetectors.

The low-cost fabrication of ZnO nanowire/CuSCN heterojunctions is demonstrated by combining chemical bath deposition with impregnation techniques. The ZnO nanowire arrays are completely filled by the CuSCN layer from their bottoms to their tops. The CuSCN layer is formed of columnar grains that are strongly oriented along the [003] direction owing to the polymeric form of the ß-rhombohedral crystalline phase. Importantly, an annealing step is found essential in a fairly narrow range of low temperatures, not only for outgassing the solvent from the CuSCN layer, but also for reducing the density of interfacial defects. The resulting electrical properties of annealed ZnO nanowire/CuSCN heterojunctions are strongly improved: a maximum rectification ratio of 2644 at ±2 V is achieved following annealing at 150 °C under air atmosphere, which is related to a strong decrease in the reverse current density. Interestingly, the corresponding self-powered UV photodetectors exhibit a responsivity of 0.02 A/W at zero bias and at 370 nm with a UV-to-visible (370-500 nm) rejection ratio of 100 under an irradiance of 100 mW/cm(2). The UV selectivity at 370 nm can also be readily modulated by tuning the length of ZnO nanowires. Eventually, a significant photovoltaic effect is revealed for this type of heterojunctions, leading to an open circuit voltage of 37 mV and a short circuit current density of 51 µA/cm(2), which may be useful for the self-powering of the complete device. These findings show the underlying physical mechanisms at work in ZnO nanowire/CuSCN heterojunctions and reveal their high potential as self-powered UV photodetectors.

Light absorption processes and optimization of ZnO/CdTe core-shell nanowire arrays for nanostructured solar cells.

The absorption processes of extremely thin absorber solar cells based on ZnO/CdTe core-shell nanowire (NW) arrays with square, hexagonal or triangular arrangements are investigated through systematic computations of the ideal short-circuit current density using three-dimensional rigorous coupled wave analysis. The geometrical dimensions are optimized for optically designing these solar cells: the optimal NW diameter, height and array period are of 200 ± 10 nm, 1-3 µm and 350-400 nm for the square arrangement with CdTe shell thickness of 40-60 nm. The effects of the CdTe shell thickness on the absorption of ZnO/CdTe NW arrays are revealed through the study of two optical key modes: the first one is confining the light into individual NWs, the second one is strongly interacting with the NW arrangement. It is also shown that the reflectivity of the substrate can improve Fabry-Perot resonances within the NWs: the ideal short-circuit current density is increased by 10% for the ZnO/fluorine-doped tin oxide (FTO)/ideal reflector as compared to the ZnO/FTO/glass substrate. Furthermore, the optimized square arrangement absorbs light more efficiently than both optimized hexagonal and triangular arrangements. Eventually, the enhancement factor of the ideal short-circuit current density is calculated as high as 1.72 with respect to planar layers, showing the high optical potentiality of ZnO/CdTe core-shell NW arrays.

Light trapping in ZnO nanowire arrays covered with an absorbing shell for solar cells.

The absorption properties of ZnO nanowire arrays covered with a semiconducting absorbing shell for extremely thin absorber solar cells are theoretically investigated by optical computations of the ideal short-circuit current density with three-dimensional rigorous coupled wave analysis. The effects of nanowire geometrical dimensions on the light trapping and absorption properties are reported through a comprehensive optical mode analysis. It is shown that the high absorptance of these heterostructures is driven by two different regimes originating from the combination of individual nanowire effects and nanowire arrangement effects. In the short wavelength regime, the absorptance is likely dominated by optical modes efficiently coupled with the incident light and interacting with the nearby nanowires (i.e. diffraction), induced by the period of core shell ZnO nanowire arrays. In contrast, in the long wavelength regime, the absorptance is governed by key optically guided modes, related to the diameter of individual core shell ZnO nanowires.

Improvement of the physical properties of ZnO/CdTe core-shell nanowire arrays by CdCl2 heat treatment for solar cells.

CdTe is an important compound semiconductor for solar cells, and its use in nanowire-based heterostructures may become a critical requirement, owing to the potential scarcity of tellurium. The effects of the CdCl2 heat treatment are investigated on the physical properties of vertically aligned ZnO/CdTe core-shell nanowire arrays grown by combining chemical bath deposition with close space sublimation. It is found that recrystallization phenomena are induced by the CdCl2 heat treatment in the CdTe shell composed of nanograins: its crystallinity is improved while grain growth and texture randomization occur. The presence of a tellurium crystalline phase that may decorate grain boundaries is also revealed. The CdCl2 heat treatment further favors the chlorine doping of the CdTe shell with the formation of chlorine A-centers and can result in the passivation of grain boundaries. The absorption properties of ZnO/CdTe core-shell nanowire arrays are highly efficient, and more than 80% of the incident light can be absorbed in the spectral range of the solar irradiance. The resulting photovoltaic properties of solar cells made from ZnO/CdTe core-shell nanowire arrays covered with CuSCN/Au back-side contact are also improved after the CdCl2 heat treatment. However, recombination and trap phenomena are expected to operate, and the collection of the holes that are mainly photo-generated in the CdTe shell from the CuSCN/Au back-side contact is presumably identified as the main critical point in these solar cells.