2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

Room temperature all-silicon photonic crystal nanocavity light emitting diode at sub-bandgap wavelengths

Silicon is now firmly established as a high performance photonic material. Its only weakness is the lack of a native electrically driven light emitter that operates CW at room temperature, exhibits a narrow linewidth in the technologically important 1300-1600 nm wavelength window, is small and operates with low power consumption. Here, an electrically pumped all-silicon nano light source around 1300-1600 nm range is demonstrated at room temperature. Using hydrogen plasma treatment, nano-scale optically active defects are introduced into silicon, which then feed the photonic crystal nanocavity to enhance the electrically driven emission in a device via Purcell effect. A narrow (Δλ=0.5 nm) emission line at 1515 nm wavelength with a power density of 0.4mW/cm2 is observed, which represents the highest spectral power density ever reported from any silicon emitter. A number of possible improvements are also discussed, that make this scheme a very promising light source for optical interconnects and other important silicon photonics applications. © 2012 by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrically Driven InAs Quantum-Dot Single-Photon Sources

Electrically driven single photon source based on single InAs quantum dot (QDs) is demonstrated. The device contains InAs QDs within a planar cavity formed between a bottom AlGaAs/GaAs distributed Bragg reflector (DBR) and a surface GaAs-air interface. The device is characterized by I-V curve and electroluminescence, and a single sharp exciton emission line at 966nm is observed. Hanbury Brown and Twiss (HBT) correlation measurements demonstrate single photon emission with suppression of multiphoton emission to below 45% at 80K

Broad-band semiconductor optical amplifiers

Broad-band semiconductor optical amplifiers (SOAs) with different thicknesses and thin bulk tensile-strained active layers were fabricated and studied. Amplified spontaneous emission (ASE) spectra and gain spectra of SOAs were measured and analyzed at different CW biases. A maximal 3 dB ASE bandwidth of 136 nm ranging from 1480 to 1616 nm, and a 3 dB optical amplifier gain bandwidth of about 90 nm ranging from 1510 to 1600 nm, were obtained for the very thin bulk active SOA. Other SOAs characteristics such as saturation output power and polarization sensitivity were measured and compared. (c) 2006 Elsevier B.V. All rights reserved.

Lifetime study of N impurity states in GaAs1-xNx (x=0.1%) under hydrostatic pressure

The lifetimes of a series of N-related photoluminescence lines (A(2)-A(6)) in GaAs1-xNx (x=0.1%) were studied under hydrostatic pressures at similar to 30 K. The lifetimes of A(5) and A(6) were found to increase rapidly with increasing pressure: from 2.1 ns at 0 GPa to more than 20 ns at 0.92 GPa for A(5) and from 3.2 ns at 0.63 GPa to 10.8 ns at 0.92 GPa for A(6). The lifetime is found to be closely correlated with the binding energy of the N impurity states, which is shown either in the pressure dependence for a given emission line or in the lifetime variation from A(2) to A(6). (c) 2006 American Institute of Physics.

Photoluminescence of rapid-thermal annealed Mg-doped GaN films

We report the investigation of temperature and excitation power dependence in photoluminescence spectroscopy measured in Mg-doped GaN epitaxial layers grown on sapphire by metalorganic chemical vapor deposition, The objective is to examine the effects of rapid-thermal annealing on Mg-related emissions. It is observed that the peak position of the 2.7-2.8 eV emission line is a function of the device temperature and annealing conditions, The phenomenon is attributed to Coulomb-potential fluctuations in the conduction and valence band edge and impurity levels due to the Mg-related complex dissociation. The blue shift of the 2.7-2.8 eV emission line with increasing excitation power provides clear evidence that a donor-acceptor recombination process underlies the observed emission spectrum. In addition, quenching of minor peaks at 3.2 and 3.3 eV are observed and their possible origin is discussed. (C) 2001 Elsevier Science Ltd. All rights reserved.

High-quality GaN grown by gas-source MBE

High-quality GaN epilayers were consistently obtained using a home-made gas-sourer MBE system on sapphire substrates. Room-temperature electron mobility of the grown GaN film is 300 cm(2)/V s with a background electron concentration as low as 2 x 10(17) cm(-3) The full-width at half-maximum of the GaN (0 0 0 2) double-crystal X-ray rocking curve is 6 arcmin. At low temperature (3.5 K), the FWHM of the: near-band-edge photoluminescence emission line is 10 meV. Furthermore, using piezoelectric effect alone with the high-quality films, two-dimensional electron gas was formed in a GaN/AlN/GaN/sapphire structure. Its room-temperature and low-temperature (77 K) electron mobility is 680 cm(2)/V s and 1700 cm(2)/V s, and the corresponding sheet electron density is 3.2 x 10(13) and 2.6 x 10(13) cm(-2), respectively. (C) 2001 Published by Elsevier Science.

Annealing effect on the surface morphology and photoluminescence of InGaAs/GaAs quantum dots grown by molecular beam epitaxy

Postgrowth rapid thermal annealing was performed on InGaAs/GaAs quantum dots grown by molecular beam epitaxy. The blue shift of the emission peak and the narrowing of the luminescence line width are observed at lower annealing temperature. However, when the annealing temperature is increased to 850 degrees C, the emission line width becomes larger. The TEM image of this sample shows that the surface becomes rough, and some large clusters are formed, which is due to the interdiffusion of In, Ga atoms at the InGaAs/GaAs interface and to the strain relaxation. The material is found to degrade dramatically when the annealing temperature is further increased to 900 degrees C, while emission from quantum dots can still be detected, along with the appearance of the emission from excited state. (C) 2000 Elsevier Science B.V. All rights reserved.

Broad-spectrum and long-lifetime emissions of Nd3+ ions in lead fluorosilicate glass

A novel Nd3+-doped lead fluorosilicate glass (NPS glass) is prepared by a two-step melting process. Based on the absorption spectrum a Judd-Ofelt theory analysis is made. The emission line width of NPS glass is 44.2nm. The fluorescence decay lifetime of the 4F3/2 level is 586±20μsec, and the stimulated emission cross-section is 0.87×10-20cm2 at 1056nm. A laser oscillation is occurred at 1062nm when pumped by 808nm Diode Laser. The slope efficiency is 23.7% with a 415mJ threshold. It is supposed that NPS glass is a good candidate for using in ultra-short pulse generation and amplification by the broad emission bandwidth and long fluorescence lifetime.

High-quality GaN grown by gas-source MBE

High-quality GaN epilayers were consistently obtained using a home-made gas-sourer MBE system on sapphire substrates. Room-temperature electron mobility of the grown GaN film is 300 cm(2)/V s with a background electron concentration as low as 2 x 10(17) cm(-3) The full-width at half-maximum of the GaN (0 0 0 2) double-crystal X-ray rocking curve is 6 arcmin. At low temperature (3.5 K), the FWHM of the: near-band-edge photoluminescence emission line is 10 meV. Furthermore, using piezoelectric effect alone with the high-quality films, two-dimensional electron gas was formed in a GaN/AlN/GaN/sapphire structure. Its room-temperature and low-temperature (77 K) electron mobility is 680 cm(2)/V s and 1700 cm(2)/V s, and the corresponding sheet electron density is 3.2 x 10(13) and 2.6 x 10(13) cm(-2), respectively. (C) 2001 Published by Elsevier Science.

Atomic Structures and Radiative Properties of He-like Ions in Debye Plasmas

A detailed investigation of plasma screening effects on atomic structure and transition properties are presented for He-like ions embedded in dense plasma environment. Multi-configuration Dirac-Fock calculations were carried out for these ions by considering a Debye-Huckel potential. A large-scale relativistic configuration-interaction method is adopted to calculate transition energies and transition probabilities and to allow for a systematic improvement of the calculations. Comparison of the presently calculated results with others, when available, is made.

Synthesis, photoluminescence, thermoluminescence and dosimetry properties of novel phosphor KSr4(BO3)(3):Ce

Polycrystalline powder sample of KSr4(BO3)(3) was synthesized by high-temperature solid-state reaction. The influence of different rare earth dopants, i.e. Tb3+, TM3+ and Ce3+, on thermoluminescence (TL) of KSr4(BO3)(3) Phosphor was discussed. The TL, photoluminescence (PL) and some dosimetric properties of Ce3+-activated KSr4(BO3)(3) phosphor were studied. The effect of the concentration of Ce3+ on TL intensity was investigated and the result showed that the optimum Ce3+ concentration was 0.2 mol%. The TL kinetic parameters of KSr4(BO3)(3):0.002 Ce3+ phosphor were calculated by computer glow curve deconvolution (CGCD) method. Characteristic emission peaking at about 407 and 383 nm due to the 4f(0)5d(1) -> F-2((5/2),(7/2)) transitions of Ce3+ ion were observed both in PL and three-dimensional (3D) TL spectra. The dose-response of KSr4(BO3)(3):0.002 Ce3+ to gamma-ray was linear in the range from 1 to 1000 mGy. In addition, the decay of the TL intensity of KSr4(BO3)(3):0.002 Ce3+ was also investigated.

Luminescence properties of rare-earth (Eu3+ and Tb3+) complexes with paraaminobenzoic acid and 1,10-phenanthroline incorporated into a silica matrix by sol-gel method

Ternary complexes of europium and terbium with paraaminobenzoic acid and 1,10-phenanthroline (Eu(p-ABA)(3). phen . 2H(2)O and Tb(p-ABA)(3). phen . 2H(2)O, where p-HABA = paraaminobenzoic acid and phen = 1,10-phenanthroline) were introduced into a silica matrix by sol-gel method. The luminescence behavior of the complexes in silica gels was studied in comparison with the. corresponding solid-state complexes by means of emission, excitation spectra, and Lifetimes. Within the range of effective dopant concentrations, the luminescence intensities of rare-earth complexes in silica gel increase with the increasing of their dopant concentration. The lifetimes of rare-earth ions (Eu3+ and-Tb3+) in silica gel doped with europium and terbium complexes become longer than those in pure complexes. Very small amounts of rare-earth complexes doped in silica gel matrix can exhibit excellent luminescence properties, (C) 1998 Elsevier Science Ltd.

Luminescence properties of the rare earth (Eu3+ and Tb3+) complexes with 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Europium and terbium complexes with 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the complexes in silica gels was studied compared with the corresponding solid state complexes by means of emission, excitation spectra and lifetimes. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Luminescence properties of rare earth (Eu3+ and Tb3+) complexes with conjugated carboxylic acids and 1,10-phenanthroline incorporated in silica matrix

Binary and ternary complexes of europium and terbium with conjugated carboxylic acid (nicotinic acid and 3,4-furandicarboxylic acid) and 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the complexes in silica gels was studied compared with the corresponding solid state complexes by means of emission, excitation spectra and lifetimes. The result indicated that the rare earth ions (EU3+ and Tb3+) showed fewer emission lines and slightly lower emission intensities in the silica gel than those in pure rare earth complexes. The lifetimes of rare earth ions (EU3+ and Tb3+) in silica gel doped with rare earth complexes became longer than those in pure rare earth complexes. (C) 1998 Elsevier Science S.A.