The use of rare-earth (RE) (e.g., Eu2+/Ce3+) ions as single luminescent centers in phosphors with tailorable emission properties has been extensively studied for their potential use in white LEDs. However, significant limitations remain, in particular, for red-emitting phosphors due to the inherently broad excitation bands which result from the underlying d–f transitions and span large parts of the visible spectral region. Guided by density functional theory calculations on the ligand structure of the non-RE Bi3+ ion, we report here on an alternative class of phosphors, [(Y,Sc)­(Nb,V)­O4:Bi3+], which exhibit homogeneous Bi3+ luminescence. In these materials, adjustment of the cation fractions enables dedicated tailoring of the excitation scheme within the spectral range of ∼340–420 nm and, in the meanwhile, allows for tunable emission spanning from about 450 nm (blue) to 647 nm (orange-red). The practical absence of any overlap between the emission and excitation spectra addresses the issues of emission color purity and visible reabsorption. Tailoring through band-gap modulation is achieved by single or parallel substitution of Nb by V and Y by Sc. Such topochemical design of the ligand configuration enables modulation of the electronic band gap and thus provides a new path toward tunable phosphors, exemplarily based on Bi3+ single doping.

We report on a red-emitting ScVO4:Bi3+ phosphor which does not show excitation at energies below 2.88 eV (430 nm). X-ray diffraction, time-resolved, and quantitative photoluminescence (PL) spectroscopy were employed to characterize relations between crystal structure and luminescence properties of the material. Results show that incorporation of Bi3+ renders the blue photoemission of blank ScVO4 to red. Dynamic luminescence analysis between 10 and 300 K reveals a complicated dependence of energy transfer from VO4 3– groups to Bi3+ ions and population redistribution of 3P1 and 3P0 of Bi3+ on temperature. This reflects in distinct changes in the luminescence decay functions. That is, a dramatic decrease of Bi3+ luminescence lifetime occurs from hundreds to only several microseconds. Density functional theory is employed to reveal how the unusual red Bi3+ luminescence comes, and results indicate that the perturbation of oxygen vacancies which is generated readily when bismuth precipitates into ScVO4 is the reason for the experimental observation, although the vacancies themselves do not show photoluminescence. Upon excitations at 330 and 380 nm, internal quantum efficiencies can be up to ∼56% and ∼47%, respectively, implying the potential application of the red phosphor in warm-white-light-emitting diodes. As a proof of concept, an exemplary device was developed by combining the present phosphor with an ultraviolet-light-emitting diode and a commercial phosphor (Ba, Eu)MgAl10O17:Mn. We obtain a color rendering index (CRI) of >90 and a color temperature of ∼4306 K at chromaticity (0.3744, 0.3991).

nanowires arrays on Au substrates were prepared by controlled air annealing of the electrodeposited Cu nanowires and furthered with dip coating.Photoelectrochemical investigations were carried out to determine their potential as photocathodes for water photo-reduction. The photocurrent of the Cu 2 O nanowires photocathode was found to be twice that of the Cu 2 O film, largely due to the higher surface area and the shorter carrier diffusion length associated with the nanowires array configuration. However, the bare Cu 2 O nanowires suffered from a significant photo-induced reductive decomposition with the electronic state of copper transferred from Cu(I) to Cu(0). By modifying the surface of the Cu 2 O nanowires with protecting layers of CuO and TiO 2 , direct contact of Cu 2 O with the electrolyte was avoided and the Cu 2 O/CuO/TiO 2 coaxial nanocable structures were found to gain a 74% higher photocurrent and 4.5 times higher stability, compared with the bare Cu 2 O nanowires array. To understand the mechanism of the improved performance, a detailed characterization and analysis on the structure, circuitry and band alignment for the Cu 2 O/CuO/TiO 2 configuration was carried out. The present study suggests a promising nanostructured photocathode configuration, which can lead to a large photocurrent with good stability against photocorrosion.

Development of coatings to minimize unwanted surface adsorption is extremely important for their use in applications, such as sensors and medical implants. Self-assembled monolayers (SAMs) are an excellent choice for coatings that minimize nonspecific adsorption because they can be uniform and have a very high surface coverage. Another equally important characteristic of such coatings is their stability. In the present study, both the bonding mechanism and the stability of stearic acid SAMs on two aluminum oxides (single-crystal C-plane aluminum oxide (sapphire) and amorphous aluminum oxide (alumina)) are investigated. The adsorption mechanism is investigated by ex situ X-ray photoelectron spectroscopy and infrared (IR) spectroscopy. The results revealed that stearic acid binds to sapphire surfaces via a bidentate interaction of carboxylate with two oxygen atoms while it binds to alumina surfaces via both bidentate and monodentate interactions. Desorption kinetics of stearic acid self-organized on both aluminum oxide surfaces into water is explored by ex situ tapping mode atomic force microscopy, IR spectroscopy, and contact angle measurements. The results exhibit that the SAMs of stearic acid formed on sapphire are not stable in water and are continuously lost through desorption. Water contact angle measurements of SAMs that are immersed in water further indicate that the desorption rate of adsorbates from atomically smooth terrace sites is substantially faster than that of adsorbates from the sites of surface defects due to weaker molecular interaction with the smooth surface. A time-dependent desorption profile of SAMs grown on amorphous alumina reveals that contact angles decrease monotonically without any regional distinction, providing further evidence for the presence of adsorption sites with different types of affinity on the amorphous alumina surface.