High-Resolution Mapping of Local Photoluminescence Properties in CuO/Cu2O Semiconductor Bi-Layers by Using Synchrotron Radiation.

The quality of a semiconductor, which strongly affects its performance, can be estimated by its photoluminescence, which closely relates to the defect and impurity energy levels. In light of this, it is necessary to have a measurement method for photoluminescence properties with spatial resolution at the sub-micron or nanoscale. In this study, a mapping method for local photoluminescence properties was developed using a focused synchrotron radiation X-ray beam to evaluate localized photoluminescence in bi-layered semiconductors. CuO/Cu2O/ZnO semiconductors were prepared on F:SnO2/soda-lime glass substrates by means of electrodeposition. The synchrotron radiation experiment was conducted at the beamline 20XU in the Japanese synchrotron radiation facility, SPring-8. By mounting the high-sensitivity spectrum analyzer near the edge of the CuO/Cu2O/ZnO devices, luminescence maps of the semiconductor were obtained with unit sizes of 0.3 µm × 0.3 µm. The devices were scanned in 2D. Light emission 2D maps were created by classifying the obtained spectra based on emission energy already reported by M. Izaki, et al. Band-like structures corresponding to the stacking layers of CuO/Cu2O/ZnO were visualized. The intensities of emissions at different energies at each position can be associated with localized photovoltaic properties. This result suggests the validity of the method for investigation of localized photoluminescence related to the semiconductor quality.

Photoelctrochemically Fabricated and Heated Cu2O/CuO Bilayers with Enhanced Photovoltaic Characteristics.

Cu2O/CuO bilayers were fabricated by electrodeposition of the CuO layer in a copper(II)-ammonia complex aqueous solution, followed by photoelectrochemical deposition of the Cu2O layer at potentials ranging from -0.3 to -1.0 V referenced to a Ag/AgCl electrode in a copper(II)-lactate complex aqueous solution under light irradiation, and the effects of varied potentials of the photoelectrochemical Cu2O depositions and post-heating conditions on their structural, optical, and photovoltaic characteristics were investigated with X-ray diffraction, field emission-scanning electron microscopy, optical absorption measurements, and external quantum efficiency (EQE) measurements with and without applied bias voltage. The Cu2O layers with a characteristic 2.1 eV band gap energy were adhesively stacked on the thorn-like grains of the CuO layers possessing a characteristic 1.5 eV band gap energy, and dense and defect-free Cu2O/CuO bilayers could be fabricated at the potentials of -0.4 and -0.5 V, but the grain size of Cu2O decreased at -0.5 V. In addition, the metallic Cu was deposited simultaneously at potentials less than -0.7 V. The Cu2O/CuO bilayer fabricated at -0.4 V revealed photovoltaic features at wavelengths ranging from 350 nm to approximately 900 nm, and a maximum EQE value of 56.8% was achieved at 510 nm in wavelength with a bias voltage of -0.1 V. The maximum EQE value, however, decreased to 1.2% accompanied with the peak wavelength shift to 580 nm, and no photovoltaic feature was observed at potentials of -0.3, -0.7, and -1.0 V. The photovoltaic performance for the Cu2O/CuO bilayer fabricated at -0.4 V was ameliorated by heating at 423 K, and the maximum EQE values were enhanced to 87.7% at 550 nm and 89.8% at 530 nm in an ambient atmosphere and vacuum. Both the Cu2O and CuO layers acted as photovoltaic layers in the Cu2O/CuO bilayer fabricated at -0.4 V and heated at 423 K, and the electrical characteristic including the carrier mobility affected the photovoltaic performance. The photovoltaic feature, however, disappeared by heating above 523 K due to the formation of nanopores inside the CuO layer and near the CuO heterointerface to the Cu2O and fluorine-doped tin oxide substrate.

Electrochemical Growth of Mg(OH) x Layered Films Stacked Parallel to the Substrates and Their Thermal Conversion to (111)-Oriented Nanoporous MgO Films.

Stacking layered metal hydroxide films parallel to a substrate is challenging. Here, we demonstrate a simple and rapid electrodeposition method for stacking magnesium hydroxide layered films. Room-temperature cathodic electrolysis (40 mA cm-2) in a Mg(NO3)2 aqueous solution induces the deposition of ⟨001⟩-oriented Mg(OH) x layered films stacked parallel to the substrate at the deposition rate of ∼2 µm min-1. The obtained Mg(OH) x layered films undergo an overall oriented transformation by heat treatment to form ⟨111⟩-oriented nanoporous MgO films.

Light-Irradiated Electrochemical Direct Construction of Cu2O/CuO Bilayers by Switching Cathodic/Anodic Polarization in Copper(II)-Tartrate Complex Aqueous Solution.

p-CuO with a band gap energy of 1.5 eV, p-Cu2O with a band gap energy of 2.05 eV, and their bilayers were prepared by controlling the potential of anodic and cathodic polarization in a copper(II)-tartrate complex aqueous solution containing copper(II) sulfate hydrate and tartaric acid in the dark and under light irradiation. Electrochemical characteristics of the electrodeposition and the resultant CuO and Cu2O layers were investigated with cyclic voltammetry, chronoamperometry, and Mott-Schottky plots, and the structural and optical characterizations were performed with X-ray diffraction, scanning electron microscopy, and optical absorption spectra measurements. The CuO layer prepared at 0.4-0.7 V was composed of aggregates of granular grains with the monoclinic lattice, and the Cu2O layer composed of coarse grains with the cubic lattice was deposited at -0.4 to 0.6 V. The flat-band potentials were estimated to be 0.145 and -0.1 V (vs Ag/AgCl) for the CuO and Cu2O layers, respectively. The 0.4 µm CuO/1.1 µm Cu2O bilayers could be prepared by switching the electrodeposition potentials of 0.4 and -0.4 V, irrespective of the presence of light irradiation. The photoelectrodeposition under light irradiation enabled the preparation of continuous and dense 1.1 µm Cu2O/0.4 µm CuO bilayer by controlling the potential, while electrodeposition in the dark led to sparse, isolated, and coarse Cu2O grains being deposited. The mechanism for the photoelectrodeposition of the bilayers was discussed based on the energy band alignment at the heterointerface to the Cu-tartrate complex solution.

Oriented Transformation from Layered Zinc Hydroxides to Nanoporous ZnO: A Comparative Study of Different Anion Types.

Thermal decomposition of layered zinc hydroxides (LZHs) is a simple and convenient way to achieve porous ZnO nanostructures. The type of anion contained in an LZH determines the fundamental characteristics of the LZH and thus affects the formation process of the resulting porous ZnO. Here we report a comparative study on the crystal orientation relationship between LZH precursors and the corresponding porous ZnO products by using well-faceted and highly oriented LZH crystals with three different anions, i.e., NO3-, SO42-, and Cl-. Highly oriented LZH crystals were prepared on layer-by-layer coated indium tin oxide substrates by electrodeposition in aqueous solution and were transformed into porous ZnO by calcination in air. The synthesized materials were characterized by X-ray diffraction, scanning electron microscopy with electron backscatter diffraction, Fourier transformed infrared spectroscopy, and X-ray photoelectron spectroscopy. The layered structure of the highly oriented LZHs was parallel to the substrate surface and all transformed to nanoporous ZnO with a ⟨0001⟩ preferred orientation. The ⟨0001⟩ orientation degree and in-plane orientation of the nanoporous ZnO differed significantly depending on the type of anion but not the decomposition temperature, revealing that the initial formation process of ZnO from the LZHs is crucial. Finally, a possible transformation mechanism explaining the difference in the resulting ZnO orientation by anions (NO3-, SO42-, and Cl-) is discussed on the basis of their layered structure and thermal decomposition processes.

Hall Effect in Bulk-Doped Organic Single Crystals.

The standard technique to separately and simultaneously determine the carrier concentration per unit volume (N, cm-3 ) and the mobility (µ) of doped inorganic single crystals is to measure the Hall effect. However, this technique has not been reported for bulk-doped organic single crystals. Here, the Hall effect in bulk-doped single-crystal organic semiconductors is measured. A key feature of this work is the ultraslow co-deposition technique, which reaches as low as 10-9 nm s-1 and enables us to dope homoepitaxial organic single crystals with acceptors at extremely low concentrations of 1 ppm. Both the hole concentration per unit volume (N, cm-3 ) and the Hall mobility (µH ) of bulk-doped rubrene single crystals, which have a band-like nature, are systematically observed. It is found that these rubrene single crystals have (i) a high ionization rate and (ii) scattering effects because of lattice disturbances, which are peculiar to this organic single crystal.

Electrodeposited ZnO-nanowire/Cu2O photovoltaic device with highly resistive ZnO intermediate layer.

Cl-doped ZnO-nanowire (Cl:ZnO-nws)/Cu2O photovoltaic devices were prepared by electrodeposition in aqueous solutions, and the effects of the insertion of the highly resistive ZnO (i-ZnO) layer has been demonstrated by an improvement of the photovoltaic performance. The Cl:ZnO-nws and i-ZnO layer were prepared by electrodeposition in a zinc chloride aqueous solution with saturated molecular oxygen and simple zinc nitrate aqueous solution, respectively. The i-ZnO layer was directly deposited on the Cl:ZnO-nws and suppressed the electrodeposition of the Cu2O layer on the Cl:ZnO-nws. The insertion of the i-ZnO layer between the Cl:ZnO-nws and Cu2O layers induced an improvement in the photovoltaic performance from 0.40 to 1.26% with a 0.35 V open circuit voltage, 7.1 mA·cm(-2) short circuit current density, and 0.52 fill factor due to the reduction of the recombination loss.

Hybrid ZnO/phthalocyanine photovoltaic device with highly resistive ZnO intermediate layer.

We report a hybrid photovoltaic device composed of a 3.3 eV bandgap zinc oxide (ZnO) semiconductor and metal-free phthalocyanine layers and the effects of the insertion of the highly resistive ZnO buffer layer on the electrical characteristics of the rectification feature and photovoltaic performance. The hybrid photovoltaic devices have been constructed by electrodeposition of the 300 nm thick ZnO layer in a simple zinc nitrate aqueous solution followed by vacuum evaporation of 50-400 nm thick-phthalocyanine layers. The ZnO layers with the resistivity of 1.8 × 10(3) and 1 × 10(8) Ω cm were prepared by adjusting the cathodic current density and were installed into the hybrid photovoltaic devices as the n-type and buffer layer, respectively. The phthalocyanine layers with the characteristic monoclinic lattice showed a characteristic optical absorption feature regardless of the thickness, but the preferred orientation changed depending on the thickness. The ZnO buffer-free hybrid 50 nm thick phthalocyanine/n-ZnO photovoltaic device showed a rectification feature but possessed a poor photovoltaic performance with a conversion efficiency of 7.5 × 10(-7) %, open circuit voltage of 0.041 V, and short circuit current density of 8.0 × 10(-5) mA cm(-2). The insertion of the ZnO buffer layer between the n-ZnO and phthalocyanine layers induced improvements in both the rectification feature and photovoltaic performance. The excellent rectification feature with a rectification ratio of 3188 and ideally factor of 1.29 was obtained for the hybrid 200 nm thick phthalocyanine/ZnO buffer/n-ZnO photovoltaic device, and the hybrid photovoltaic device possessed an improved photovoltaic performance with the conversion efficiency of 0.0016%, open circuit voltage of 0.31 V, and short circuit current density of 0.015 mA cm(-2).

Hybrid Cu(2)O diode with orientation-controlled C(60) polycrystal.

We report on a hybrid diode composed of a 2.1 eV bandgap p-cupric oxide (Cu2O) semiconductor and fullerene (C60) layer with a face-centered cubic configuration. The hybrid diode has been constructed by electrodeposition of the 500 nm thick Cu2O layer in a basic aqueous solution containing a copper acetate hydrate and lactic acid followed by a vacuum evaporation of the 50 nm thick C60 layer at the evaporation rate from 0.25 to 1.0 Å/s. The C60 layers prepared by the evaporation possessed a face-centered cubic configuration with the lattice constant of 14.19 A, and the preferred orientation changed from random to (111) plane with decrease in the C60 evaporation rate from 1.0 to 0.25 Å/s. The hybrid p-Cu2O/C60 diode showed a rectification feature regardless of the C60 evaporation rate, and both the rectification ratio and forward current density improved with decrease in the C60 evaporation rate. The excellent rectification with the ideality factor of approximately 1 was obtained for the 500 nm thick (111)-Cu2O/50 nm thick (111)-fcc-C60/bathocuproine (BCP) diode at the C60 evaporation rate of 0.25 Å /s. The hybrid Cu2O/C60 diode prepared by stacking the C60 layer at the evaporation rate of 0.25 Å/s revealed the photovoltaic performance of 8.7 × 10(-6)% in conversion efficiency under AM1.5 illumination, and the conversion efficiency changed depending on the C60 evaporation rate.

Preparation of core/shell and hollow nanostructures of cerium oxide by electrodeposition on a polystyrene sphere template.

Core/shell nanostructures of polystyrene (PS)/CeO2 have been prepared on conductive glass substrates by using a novel electrochemical route consisting of (i) the electrophoretic deposition of a PS sphere monolayer on the substrate and (ii) the following potentiostatic electrodeposition of CeO2 on the PS sphere template in Ce(NO3)3 aqueous solutions. The structural morphologies of the deposit changed drastically depending on the Ce(NO3)3 concentration; i.e., spherical and needlelike shells were deposited. The deposit was formed only on the PS sphere surface because of an interaction between cationic cerium species and a sulfate group that was immobilized on the PS sphere surface. The spherical shell layer was assigned as CeO2, and the needlelike shells were composed of Ce(OH)3 needles formed on the CeO2 layer surface, indicating that the deposit species changes from CeO2 to Ce(OH)3 during electrodeposition only in a 1 mM Ce3+ solution. Deposition of Ce(OH)3 would begin when electrogenerated hydrogen peroxide was consumed by decomposition under reductive conditions and could no longer oxidize Ce3+ ions. The corresponding CeO2 hollow shells were obtained by thermal elimination of the PS sphere core and transformation of Ce(OH)3 into CeO2 while keeping their original shapes.

Light-assisted chemical deposition of highly (0001) oriented zinc oxide film.

Highly (0001) oriented zinc oxide (ZnO) films of smooth layer type and hexagonal columns have been prepared on quartz glass substrates at temperature as low as 323 K by UV light assisted chemical deposition from an aqueous solution containing hydrated zinc nitrate and dimethylamine-borane (DMAB).