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Enhancing Light Harvesting by Hierarchical Functionally Graded Transparent Conducting Al-doped ZnO Nano- and Mesoarchitectures

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 Publication date 2013
  fields Physics
and research's language is English




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A functionally graded Al-doped ZnO structure is presented which combines conductivity, visible transparency and light scattering with mechanical flexibility. The nano and meso-architecture, constituted by a hierarchical, large surface area, mesoporous tree-like structure evolving in a compact layer, is synthesized at room temperature and is fully compatible with plastic substrates. Light trapping capability is demonstrated by showing up to 100% improvement of light absorption of a low bandgap polymer employed as the active layer.



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The structure-property relation of nanostructured Al-doped ZnO thin films has been investigated in detail through a systematic variation of structure and morphology, with particular emphasis on how they affect optical and electrical properties. A variety of structures, ranging from compact polycristalline films to mesoporous, hierarchically organized cluster assemblies, are grown by Pulsed Laser Deposition at room temperature at different oxygen pressures. We investigate the dependence of functional properties on structure and morphology and show how the correlation between electrical and optical properties can be studied to evaluate energy gap, conduction band effective mass and transport mechanisms. Understanding these properties opens the way for specific applications in photovoltaic devices, where optimized combinations of conductivity, transparency and light scattering are required.
ZnO-based scintillation ceramics for application in HENPA LENPA analyzers have been investigated. The following ceramic samples have been prepared: undoped ones (ZnO), an excess of zinc in stoichiometry (ZnO:Zn), doped with gallium (ZnO:Ga) and lithium (ZnO:Li). Optical transmission, x-ray excited emission, scintillation decay and pulse height spectra were measured and analyzed. Ceramics have reasonable transparency in visible range (up to 60% for 0.4 mm thickness) and energy resolution (14.9% at 662 keV Cs137 gamma excitation). Undoped ZnO shows slow (1.6 {mu}s) luminescence with maximum at 2.37 eV and light yield about 57% of CsI:Tl. ZnO:Ga ceramics show relatively low light yield with ultra fast decay time (1 ns). Lithium doped ceramics ZnO:Li have better decay time than undoped ZnO with fair light yield. ZnO:Li ceramics show good characteristics under alpha-particle excitation and can be applied for the neutral particle analyzers.
We have studied the electronic structure of Zn$_{0.9}$Fe$_{0.1}$O nano-particles, which have been reported to show ferromagnetism at room temperature, by x-ray photoemission spectroscopy (XPS), resonant photoemission spectroscopy (RPES), x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD). From the experimental and cluster-model calculation results, we find that Fe atoms are predominantly in the Fe$^{3+}$ ionic state with mixture of a small amount of Fe$^{2+}$ and that Fe$^{3+}$ ions are dominant in the surface region of the nano-particles. It is shown that the room temperature ferromagnetism in the Zn$_{0.9}$Fe$_{0.1}$O nano-particles is primarily originated from the antiferromagnetic coupling between unequal amounts of Fe$^{3+}$ ions occupying two sets of nonequivalent positions in the region of the XMCD probing depth of $sim$ 2-3 nm.
La-doped SrSnO3 (LSSO) is known as one of deep-ultraviolet (DUV)-transparent conducting oxides with an energy bandgap of ~4.6 eV. Since LSSO can be grown heteroepitaxially on more wide bandgap substrates such as MgO (Eg ~7.8 eV), LSSO is considered to be a good candidate as a DUV-transparent electrode. However, the electrical conductivity of LSSO films are below 1000 S cm^-1, most likely due to the low solubility of La ion in the LSSO lattice. Here we report that high electrically conducting (>3000 S cm^-1) LSSO thin films with an energy bandgap of ~4.6 eV can be fabricated by pulsed laser deposition on MgO substrate followed by a simple annealing in vacuum. From the X-ray diffraction and the scanning transmission electron microscopy analyses, we found that lateral grain growth occurred during the annealing, which improved the activation rate of La ion, leading to a significant improvement of carrier concentration (3.26 x 10^20 cm^-3) and Hall mobility (55.8 cm^2 V^-1 s^-1). The present DUV-transparent oxide semiconductor would be useful as a transparent electrode for developing optoelectronic devices, which transmit and/or emit DUV-light.
Low-temperature heat capacities (Cp) of nanostructured rock salt (rs-ZnO) and wurtzite (w-ZnO) polymorphs of zinc oxide were measured in the 2-315 K temperature range. No significant influence of nanostructuring on Cp of w-ZnO has been observed. The measured Cp of rock salt ZnO is lower than that of wurtzite ZnO below 100 K and is higher above this temperature. Using available thermodynamic data, we established that the equilibrium pressure between nanocrystalline w-ZnO and rs-ZnO is close to 4.6 GPa at 300 K (half as much as the onset pressure of direct phase transformation) and slightly changes with temperature up to 1000 K.
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