SENSITIZATION OF PHOTOCONDUCTIVE EFFECTS IN ZINC OXIDE*,†

Abstract— The current status of research on sensitized photoconductive effects in zinc oxide is reviewed. The various types of chemical and spectral photosensitization processes observed in polycrystalline specimens can be explained qualitatively with a generalized electron acceptor molecule (EAM) model. in which electronegative surface agents trap zinc oxide conduction electrons in the dark and illumination causes a release of the trapped electrons. The EAM may be an adsorbed gas or vapor, adsorbed dye molecules, or an aggregated dye film, depending on the particular photoeffect.     

Studies of interface phonons

The vibrational modes localized at the interface between two distinct crystals have been studied for a simple crystal model obeying all of the invariance conditions required for models used in studies of dynamical properties of crystal surfaces, and giving rise to Rayleigh surface waves. The two crystals are assumed to be semi-infinite simple cubic and to have the same lattice parameter a. They differ by their mass (M and M_A) and the central force interactions between first (K and K_a) and second nearest neighbors $\text{1}\text{2}\text{K}$ and $\text{1}\text{2}\text{K}{}_{\mathrm{A}}$. The interface is obtained by coupling the (001) free surfaces of these distinct crystals by central force intractions (K^'). We find that the variation of the interaction conditions (K^') at the interface and of the $\text{(}\text{K}\text{M}\text{)}\text{(}\text{K}{}_{\mathrm{A}}\text{M}{}_{\mathrm{A}}\text{)}$ parameter has the following qualitative effects on the properties of surface and bulk phonons. When (K^') increases from zero to a finite value, the frequencies of the surface phonons increase and are splitted in the case of two identical crystals. One can say that the surface phonons are transformed into interface modes. For some values of $\text{K}{}^{\mathrm{\text{'}}}\text{K}$ and $\text{(}\text{K}\text{M}\text{)}\text{(}\text{K}{}_{\mathrm{<mtext>A</mtext>}}\text{M}{}_{\mathrm{<mtext>A</mtext>}}\text{)}$ parameters these interface phonons may be admixed with bulk phonons and thus become virtual interface states.     

Interaction of cobalt(II) and nickel(II) with a gamma-linked, bis-beta-diketone ligand to yield an unusual coordination motif

Discrete cobalt(II) and nickel(II) complexes of type ML (where L is a bis(2,4-pentanedionate) derivative incorporating a -SCH2CH2S- bridge between the gamma-carbons of respective beta-diketone units) have been synthesised and represent the first examples in which a gamma-substituted, thioether-containing beta-diketone ligand coordinates via a sulfur and oxygen donor in preference to the classical coordination mode involving both beta-diketonate oxygens.     

Lanthanide luminescent switches: modulation of the luminescence of bis-macrocyclic based Tb(III) conjugates in water by H+, Na+ and K+

The synthesis of four bis-macrocyclic conjugates made from the coupling of either diaza-15-crown-5 ethers (1 and 3) and diaza-18-crown-6 ethers (2 and 4) to either amide or carboxylate functionalized cyclen (1,4,7,10-tetraazacyclododecane), and their corresponding cationic Tb(III) complexes, Tb-1, Tb-2, and neutral complexes Tb-3 and Tb-4 are described. The effect on the ground, singlet excited states and the Tb(III) emission, was investigated either as a function of pH or the concentration of several Group I and II cations, upon excitation at 300 nm. The ground state and singlet excited states of the Tb(III) complexes were found to be modulated by ions such as H+, Na+ or K+, signifying the recognition of these ions by the crown ether receptors. In acidic media, below pH 4, the Tb(III) emission was highly pH sensitive, gradually increasing with large orders of magnitude of luminescence enhancements. For Tb-1 and Tb-2 complexes, the Tb(III) emission was also "switched on" in alkaline media above pH 8. At pH 7.4, the recognition of Na+ or K+ also gave rise to a significant change in the Tb(III) emission due to the modulation of the antenna-receptor moieties by these ions. For Tb-1 and Tb-3 the largest changes were seen for Na+, whereas for Tb-2 and Tb-4 the largest changes were seen for K+.