We propose a widegap II–VI semiconductor alloy, MgxZn1−xO, for the fabrication of heteroepitaxial ultraviolet light emitting devices based on ZnO. The c-axis oriented MgxZn1−xO films were epitaxially grown by pulsed laser deposition on ZnO epitaxial films and sapphire (0001) substrates using ceramic targets. Solid solution films were prepared with Mg content up to x=0.33, achieving a band gap of 3.99 eV at room temperature. MgO impurity phase segregated at x⩾0.36. Lattice constants of MgxZn1−xO films changed slightly (∼1%), increasing in a axis and decreasing in c-axis direction with increasing x. These films showed ultraviolet photoluminescence at energies from 3.36 (x=0) to 3.87 eV (x=0.33) at 4.2 K.
Room-temperature ultraviolet ͑UV͒ laser emission of ZnO microcrystallite thin films is reported. The hexagonal ZnO microcrystallites are grown by laser molecular beam epitaxy. They are self-assembled and parallelly arrayed on sapphire substrates. The facets of the hexagons form natural Fabry-Pérot lasing cavities. The optical gain for the room-temperature UV stimulated emission is of an excitonic nature and has a peak value an order of magnitude larger than that of bulk ZnO crystal. The observation of room-temperature UV lasing from the ordered, nano-sized ZnO crystals represents an important step towards the development of nanometer photoelectronics.
We studied the UV-vis absorption and fluorescence in solution/solid states of [n]cycloparaphenylene ([n]CPP: n = 9, 12, 14, 15, and 16), and conducted theoretical studies to better understand the experimental results. The representative experimental findings include (i) the most intense absorption maxima (λ(abs1)) display remarkably close values (338-339 nm), (ii) the longest-wavelength absorption maxima (λ(abs2)) are blue-shifted with increasing the ring size (395 → 365 nm), (iii) the emission maxima (λ(em)) are blue-shifted with increasing the ring size (494 → 438 nm for longest-wavelength maxima), (iv) the fluorescent quantum yields (Φ(F)) in solution are high (0.73-0.90), (v) the fluorescence lifetimes (τ(s)) of [9]- and [12]CPP are 10.6 and 2.2 ns, respectively, and (vi) the Φ(F) values slightly increase in polymer matrix but significantly decrease in the crystalline state. According to TD-DFT calculations, the longest-wavelength absorption (λ(abs2)) corresponds to a forbidden HOMO → LUMO transition and the most intense absorption (λ(abs1)) corresponds to degenerate HOMO - 1 → LUMO and HOMO → LUMO + 1 transitions with high oscillator strength. The interesting and counterintuitive optical properties of CPPs (constant λ(abs1) and blue shift of λ(abs2)) could be ascribed mainly to the ring-size effect in frontier molecular orbitals (in particular the increase of the HOMO-LUMO gap as the number of benzene rings increases). On the basis of comparative calculations using hypothetical model geometries, we conclude that the unique behavior of HOMO and LUMO of CPPs is due mainly to their lack of a conjugation length dependence in combination with a significant bending effect (particularly to HOMO) and a torsion effect (particularly to LUMO).
We describe the structural and optical properties of II-VI oxide alloys, Mg x Zn 1Ϫx O and Cd y Zn 1Ϫy O, grown by pulsed-laser deposition. Single-phase alloyed films of ͑Mg,Zn͒O and ͑Cd,Zn͒O with c-axis orientations were epitaxially grown on sapphire ͑0001͒ substrates. The maximum magnesium and cadmium concentrations ͑xϭ0.33 and yϭ0.07, respectively͒ were significantly larger than the thermodynamic solubility limits. The band gap energies systematically changed from 3.0 (yϭ0.07) to 4.0 eV (xϭ0.33) at room temperature. The photoluminescence peak energy deduced at 4.2 K could be tuned from 3.19 to 3.87 eV by using Cd 0.07 Zn 0.93 O and Mg 0.33 Zn 0.67 O at both ends, respectively. The lattice constants of the a axis were monotonically increasing functions of the concentrations of both alloys. The exciton-phonon coupling strength was determined in Cd 0.01 Zn 0.99 O grown on a lattice-matched ScAlMgO 4 substrate.
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