Photoactivity of anatase–rutile TiO2 nanotubes formed by anodization method

Titania (TiO₂) nanotubes were prepared by anodizing titanium (Ti) foils in an electrochemical bath consisting of 1 M glycerol with 0.5 wt.% NH₄F.The pH of the bath was kept constant at 6 and the anodization voltage was varied from 5 V, 20 V to 30 V. It is found that the morphology of the anodized titanium is a function of anodization voltage with pits-like oxide formed for the sample made at 5 V and samples made at 20 V and 30 V consisted of well-aligned nanotubes growing perpendicularly on the titanium foil. However, the nanotubes formed on the samples made at 30 V were not uniform in terms of the nanotubes' diameter and wall thickness. Regardless of the anodization voltage, as anodised samples were amorphous. The crystal structure evolution was studied as a function of annealing temperatures and was characterised by X-ray diffraction and Raman spectroscopy analyses. Crystallization of the nanotubes to anatase phase occurred at 400 °C while rutile formation occurred at 700 °C. Disintegration of the nanotube arrays was observed at 600 °C and the structure completely vanished at 700 °C. TiO₂ nanotube annealed at 400 °C and containing 100% anatase revealed the highest photocatalytic activity for the degradation of methyl orange. Consequently, these results indicate that diameter, wall thickness, crystal structure and degree of crystallinity of the TiO₂ nanotube arrays are the important factors influencing the efficiency of the photocatalytic activity.     

Green synthesis of bi-component copper oxide composites and enhanced photocatalytic performance

A facile and green route was proposed for the synthesis of bi-component copper oxide composite without any templates and additives. The effects of D-(+)-glucose amount, reaction temperature, and reaction time on the morphology and constitution of the products were investigated by SEM, X-ray diffraction, and UV-vis DRS in detail. The results indicate that a series of Cu₂O–CuO bi-component copper oxide composites with various morphologies can be easily obtained. Structure characterisation and photocatalytic tests show that the bi-component Cu₂O–CuO composites exhibited better photodecolouration of methylene blue than those of the Cu₂O, CuO, and Cu–CuO compounds owing to the existence of the synergistic effect between the CuO and Cu₂O.     

High-rate reduction of copper oxide using atmospheric-pressure inductively coupled plasma microjets

Reduction of copper oxide was performed using an atmospheric-pressure inductively coupled plasma (AP-ICP) microjet while varying the input power P between 15 and 50 W. Cuprous oxide (Cu₂O) and cupric oxide (CuO) were formed on the sputtered Cu surface by thermal annealing. Dynamic behavior of the microplasma jet, optical emission from H atoms, the substrate temperature, chemical bonding states of the treated surface, and the thickness of the reduced Cu layer were measured to study the fundamental reduction process. Surface composition and the thickness of the reduced Cu layer changed significantly with P. Rapid reduction of CuO and Cu₂O was achieved at a rate of 493 nm/min at P = 50 W since high-density H atoms were produced by the AP-ICP microjet.     

Electrochemical reduction of CO2 by Cu2O-catalyzed carbon clothes

Cu₂O cubes with average edge lengths of 640 nm were prepared by a chemical reduction approach. The as-synthesized Cu₂O particles were deposited on carbon clothes for electrochemical characterizations in cyclic voltammetry (CV) and potentiostatic measurements. In 0.5 M NaOH electrolytes saturated with N₂ or CO₂, both the Cu₂O and carbon clothes were stable at the potential range of 0 to − 1.7 V. Comparisons in the current responses from the CV and potentiostatic measurements suggested the Cu₂O with notable catalytic abilities for the CO₂ reduction. The mass activity was estimated at 0.94 mA/mg. Chemical analysis from gas chromatography confirmed the methanol to be the predominant product.     

Preparation and characterization of Cu3Sn nanoparticles via a facile ultrasonic irradiation

Cu₃Sn nanoparticles were prepared with ease by allowing bulk tin to react with copper acetate under ultrasonic irradiation. The microstructure and thermal stability of resultant Cu₃Sn nanoparticles were analyzed by means of transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). In the meantime, the possible growing mechanism of Cu₃Sn nanoparticles was presented; and the tribological properties of Cu₃Sn nanoparticles as lubricating additives were evaluated. It has been found that as-synthesized hexagonal Cu₃Sn nanoparticles are of spherical shape and have a narrow size distribution and an average diameter of 90 nm. The growth of Cu₃Sn nanoparticles involves three stages of ultrasonic dispersion, reaction and surface modification. Besides, ultrasonic irradiation in combination with surface-capping by oleic acid contributes to prevent on-growing Cu₃Sn nanoparticles from aggregation, making it feasible for Cu₃Sn nanoparticles to be well dispersed in lubricating base stock and significantly increase the antiwear ability and load-carrying capacity of liquid paraffin.     

Fabrication and characterization of self-organized mixed oxide nanotube arrays by electrochemical anodization of Ti-6Al-4V alloy

Self-organized mixed oxide nanotube arrays were fabricated by anodization of Ti-6Al-4V alloy in H₃PO₄/NH₄F aqueous solution. The nanotubes of 90-180 nm in diameter and 10-20 nm in wall thicknesses could be tuned by changing anodization voltages. Whereas, the as-prepared nanotube arrays were amorphous; to induce crystallinity, the products were annealed at 400 °C, 500 °C and 600 °C, respectively. The UV-Vis spectra of samples annealed at 600 °C gives the maximum absorption in the visible spectra range. Various characterization techniques (viz., FESEM, XPS, XRD, and UV-Vis) were used to study the morphology, composition, phase and band gap of the films.     

A Two-step anodization to grow high-aspect-ratio TiO2 nanotubes

High-aspect-ratio TiO₂ nanotubes with small diameter are favored in dye-sensitized solar cells for large dye loading provided by high surface areas. However, long TiO₂ nanotubes with small diameter are difficult to grow under usual anodizing conditions due to unavoidable chemical dissolution of the top portion of the as-fashioned tubes. In the present work, two kinds of double-layered TiO₂ nanotube arrays were prepared by changing voltage from high to low (i.e., from 30 V to 15 V) or from low to high (i.e., from 15 V to 30 V). It is found that the top layer can serve as a sacrificial layer to protect the continuous growth of the bottom layer from chemical dissolution. Accordingly, the two-step anodization from high voltage to low voltage is proposed to produce high-aspect-ratio TiO₂ nanotubes with small diameter underneath a sacrificial top layer.     

Fabrication of TiO2 nanotubes by anodization of Ti thin films for VOC sensing

Ti thin films were anodized in aqueous HF (0.5 wt.%) and in polar organic (0.5 wt.% NH₄F + ethylene glycol) electrolytes to form TiO₂ nanotube arrays. Ti thin films were deposited on microscope glass substrates and then anodized. Anodization was performed at potentials ranging from 5 V to 20 V for the aqueous HF and from 20 V to 60 V for the polar organic electrolytes over the temperatures range from 0 to 20 °C. The TiO₂ nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX). It has been observed that anodization of the deposited Ti thin films with aqueous HF solution at 0 °C resulted in nanotube-type structures with diameters in the range of 30-80 nm for an applied voltage of 10 V. In addition, the nanotube-type structure is observed for polar organic electrolyte at room temperature at the anodization voltage higher than 40 V. The volatile organic compound (VOC) sensing properties of TiO₂ nanotubes fabricated using different electrolytes were investigated at 200 °C. The maximum sensor response is obtained for carbon tetrachloride. The sensor response is dependent on porosity of TiO₂. The highest sensor response is observed for TiO₂ nanotubes which are synthesized using aqueous HF electrolyte and have very high porosity.     

Morphology-dependent antibacterial activities of Cu2O

Cubic and octahedral Cu₂O microcrystals were synthesized by the reduction of a copper-ligand complex solution with glucose under microwave irradiation using ethylenediaminetetraacetic acid (EDTA) and N,N,N′,N′-tetramethyl ethylenediamine (TMEDA) as ligands. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) confirmed that the surfaces of the cubic and octahedral of Cu₂O microcrystals had {100} and {111} lattice planes. The antibacterial activity of the Cu₂O microcrystals against E. coli was examined using optical density (OD) methods. The antibacterial activity of the cubic Cu₂O crystals was superior to that of the octahedral Cu₂O crystals. The mechanism of the specific morphology-controlled synthesis of Cu₂O and their morphology-dependent antibacterial activity are discussed.     

Preparation and characterization of TiO2/polystyrene core-shell nanospheres via microwave-assisted emulsion polymerization

A combined procedure of sol-gel and microwave-assisted emulsion polymerization has been developed to prepare TiO₂/polystyrene core-shell nanospheres with nano-scale TiO₂ core and smooth and well-defined polystyrene shell. The core-shell structure and morphology were examined by TEM. The diameter and its distribution of the nanospheres were measured by dynamic light scattering. The nanospheres were characterized with Fourier transform infrared spectroscopy (FTIR). It is found that the diameter and its distribution of the TiO₂/polystyrene core-shell nanospheres can be regulated by the concentration of styrene monomer in the emulsion solution.     

Tuning the electronic structure of the transparent conducting oxide Cu2O

The electronic structure of Cu₂O is important for its application as a p-type transparent conducting oxide (TCO). To be useful as a TCO, a material needs to show enhanced transparency in the visible range (band gap > 3 eV) as well as good conduction properties. While Cu₂O has too small a band gap, alloys of Cu₂O and Al₂O₃ or Cu₂O and alkaline earth oxides are known to display enhanced transparency, with little degradation of electrical properties. It is of interest to consider how to dope Cu₂O p-type, e.g. Cu vacancies (oxidation) or cationic dopants. We present a study of the electronic structure and effective hole masses of stoichiometric and oxidised Cu₂O and study metal cation doping, using density functional theory (DFT), to analyse p-type doping scenarios. We show that formation of a Cu vacancy is relatively facile, introducing delocalised hole states, with a light hole present. Substitutional cation doping with Al and Au/Ag is found to decrease the band gap but maintains a light hole effective mass necessary for p-type conduction.     

Thermodynamic modeling of the initial microstructural evolution of oxide films grown on bare copper

A thermodynamic model is presented that predicts the initial growth of either a (semi-) coherent crystalline oxide phase or an amorphous oxide phase (with a subsequent amorphous-to-crystalline transition) on a bare metal as function of the substrate orientation, growth temperature and film thickness. The model accounts for possible relaxation of growth stresses by plastic deformation. The direct formation and growth of semi-coherent, crystalline Cu₂O is predicted by application of the model to oxide overgrowth on bare Cu{111}, Cu{100} and Cu{110}. For oxide overgrowths on Cu{111} and Cu{110}, a square grid of misfit dislocations with a dislocation distance of about six Cu₂O unit cells would occur on the basis of the model calculations, which agrees with experimental observations reported for Cu{111} in the literature. On Cu{100} an array of misfit dislocations is formed along the single direction of high lattice mismatch.     

On the surface analysis of copper oxides: the difficulty in detecting Cu3O2

The existence of Cu₃O₂, a gross defect structure of Cu₂O, has been documented experimentally since the early 1960s. However, discussions of the oxidation of copper often neglect the importance of this phase; in fact, it is often omitted entirely from such discussions. This results from the difficulty in determining the chemical state during sputter depth profiling and relying on techniques that have difficulty providing chemical state information. The occurrence of sputter reduction during the depth profiling of copper oxide layers has been demonstrated with XPS depth profiles on a series of copper samples oxidized, for varying lengths of time, in air at a temperature of either 423 or 523 K. Under these conditions, a thin layer of CuO/Cu(OH)₂ terminates the oxide layers. Beneath this layer, the presence of Cu₃O₂ is expected on the samples prepared at 423 K. However, immediately upon the beginning of sputtering, only Cu¹⁺ is detected in the oxide layers. A zone of constant Cu:O ratio of (approximately ∼1.5) is found throughout most of the oxide layer even though Cu²⁺ is not detected. On the samples prepared at 523 K, the presence of CuO is anticipated. However, Cu²⁺ is not detected after sputtering is initiated and a region of constant Cu:O ratio of ca. 1.5 is detected. The inherent difficulties involved in investigating oxide layer growth and vertical oxide layer structure using sputter depth profiling are discussed in light of this experimental data.     

Optoelectronic properties of sputter-deposited Cu2O-Ag-Cu2O treated with rapid thermal annealing

Cu₂O and two types of Cu₂O-Ag-Cu₂O (CAC) multilayered thin films were deposited on glass substrates using DC-magnetron sputtering. For CAC films, the mass thickness of Ag layer was controlled at 3 nm. After deposition, some of these films were annealed using a rapid thermal annealing (RTA) system at 650 °C, in order to create embedded Ag particles. AC films were used to study the clustering effect of Ag in Ar atmosphere, as well as for forming the 2nd type of CAC film by covering another Cu₂O layer on the annealed AC structure. A UV-VIS-NIR photometer, a Hall measurement system, and a I-V measurement system were used to characterize the optical and electrical properties of these films with and without RTA. The results show that 2-dimensional Ag layer can transform into many individual particles due to its high surface tension at annealing temperature, no matter when the annealing was carried out. For CAC films, without annealing, the optical transmission and the resistivity are decreased with the inserted Ag layer. After annealing, both the transmission and resistivity are increased, possibly due to the clustering effect of Ag layer. Most importantly, it is found that the embedded Ag particles can increase the light absorption in the NIR-IR region, which can increase photo-induced current.     

Effect of annealing on the electrodeposited Cu2O films for photoelectrochemical hydrogen generation

Cu₂O films were electrodeposited on stainless steel substrates followed by Ar annealing for photoelectrochemical hydrogen generation. Plating variables including time and pH for the plating bath were explored to obtain desirable film qualities. X-ray diffraction (XRD) patterns indicated that the as-deposited Cu₂O films exhibited preferred orientations in (200) and (111) planes from the plating bath of pH 9 and pH 11, respectively. Images from scanning electron microscope (SEM) revealed pyramid-like grains in 1 µm size for the Cu₂O films from pH 9 plating bath and large plate-like grains in 3-8 µm size from pH 11 plating bath. Identical results from SEM and XRD were obtained from the Cu₂O films at longer plating time. After annealing at 350 °C for 30 and 60 min, the Cu₂O phase was nicely maintained but SEM images demonstrated coarser grains. Photoelectrochemical activity for H₂ generation was obtained on the Cu₂O films before and after annealing by recording relevant photoelectrochemical currents at − 0.3 V in 0.5 M aqueous Na₂SO₄ solution. For the Cu₂O films from both baths, substantial increments in photoelectrochemical current were observed for the annealed samples as opposed to as-deposited ones. The largest photoelectrochemical current was obtained at 0.143 mA/cm² from the Cu₂O film of pH 9 plating bath with 60 min annealing, which exhibited a 560% increase over the as-deposited sample. We attributed the enhanced photoelectrochemical current to the improved crystallinity and reduced defects for the annealed Cu₂O films.     

Mechanisms of carrier generation and transport in Ni-doped Cu2O

The density and mobility of hole carriers in Ni-doped and undoped cuprous oxide (Cu₂O) films prepared by pulsed laser deposition (PLD) from Ni-doped and undoped CuO targets, respectively, were measured in order to examine the mechanisms of carrier generation and transport in doped films. The temperature dependence of the carrier density of the films revealed that regardless of the Ni content, the activation energies of the acceptor level of the films are 0.22-0.25 eV. The temperature dependence of the mobility of the films changed from −0.58 to ∼0 by doping with Ni. These results evidenced that hole carriers in Ni-doped Cu₂O as well as in undoped Cu₂O were generated by Cu vacancies and were primarily scattered by neutral impurity scattering centers. X-ray diffraction (XRD) measurements of the films showed that the mass fraction of Cu₂O in the films decreased with increasing Ni content, while that of CuO increased. It was also found that the reduction process of CuO to Cu₂O was suppressed by the Ni doping.     

Photoluminescence and Raman study of Cu2ZnSn(SexS1 − x)4 monograins for photovoltaic applications

The quaternary semiconductors Cu₂ZnSnSe₄ and Cu₂ZnSnS₄ have attracted a lot of attention as possible absorber materials for solar cells due to their direct bandgap and high absorption coefficient (> 10⁴ cm⁻¹). In this study we investigate the optical properties of Cu₂ZnSn(Se_xS_1 − x)₄ monograin powders that were synthesized from binary compounds in the liquid phase of potassium iodide (KI) flux materials in evacuated quartz ampoules. Radiative recombination processes in Cu₂ZnSn(Se_xS_1 − x)₄ monograins were studied by using low-temperature photoluminescence (PL) spectroscopy. A continuous shift from 1.3 eV to 0.95 eV of the PL emission peak position with increasing Se concentration was observed indicating the narrowing of the bandgap of the solid solutions. Recombination mechanisms responsible for the PL emission are discussed. Vibrational properties of Cu₂ZnSn(Se_xS_1 − x)₄ monograins were studied by using micro-Raman spectroscopy. The frequencies of the optical modes in the given materials were detected and the bimodal behaviour of the A₁ Raman modes of Cu₂ZnSnSe₄ and Cu₂ZnSnS₄ is established.     

Shape controlled synthesis and characterization of Cu2O nanostructures assisted by composite surfactants system

A simple methodology has been demonstrated to synthesize various nanocrystalline Cu₂O materials assisted by composite surfactant system, SDS and Tween 80 using the polyol method. Glycolaldehyde prepared in situ by heating ethylene glycol solvent at 160 °C for 2 h, was utilized as the reducing agent. The relative ratio of the two surfactants was manipulated to achieve different Cu₂O morphologies, e.g. nanocrystalline Cu₂O flowers, hollow spheres consisting of holes and ring type structure. The FT-IR spectroscopy confirmed that the SDS and Tween 80 moieties were indeed present on the surface as capping agents in order to stabilize the surface nanocrystallites by the co-ordinative interactions between the oxygen atoms of Tween 80 and SDS and the Cu atoms at the surface of the synthesized Cu₂O particles. These oxygen atoms eventually encourage the oxidation of the surface Cu atoms to form a thin CuO layer, presence of which on the surface was corroborated by the XPS measurements. Sputtering of the samples was also carried out to remove the surface CuO thin layer and expose the inner Cu₂O. These nanomaterials were then investigated for their potential applications in photocatalytic degradation of Rhodamine B dye.     

Repeatable synthesis of Cu2O nanorods by a simple and novel reduction route

Cu₂O nanorods were synthesized by reducing bamboo leaf-shaped Cu(OH)₂ with sodium hypophosphite (NaH₂PO₂) in an H₂O/ethylene glycol (EG) mixing solution. The Cu(OH)₂ was prepared by adding an alkaline solution to an aqueous solution containing CuSO₄ and NaH₂PO₂ at room temperature. The optimum temperature range for the reduction of the Cu(OH)₂ to Cu₂O nanorods was 55-70 °C. The products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. The result showed the prepared Cu₂O nanorods were uniform and had diameters of 10-20 nm and lengths of 150-200 nm. The synthesis is simple, inexpensive, and highly repeatable.     

Cryogenic STM/STS observation on oxide superconductors

The topographic and electronic properties of the surfaces of (001) and (110) oriented YBa₂Cu₃O_y, epitaxial films have been probed by atomic resolution STM/STS at 4.2 K. The STM image on the (001) surface clearly revealed the atomic corrugation of the tetragonal lattice with an average spacing of 0.4 nm. while on the (110) surface the orthorhombic atomic lattice, corresponding to the Cu atoms of both CuO₂ and CuO chain planes, was observed. The STS result on the (001) surface indicated the semiconducting nature of the terminating layer. As the tunneling tip came closer to the surface, however, the shape of the tunneling spectrum became more metallic and showed a superconducting energy gap, which seems to arise from the underlying superconducting layer. On the other hand, the tunneling spectra on the (110) surface indicated superconducting gap structures, independent of the tip-sample distance.