Stephen C. Rand

Optical properties of silicon nitride films deposited by hot filament chemical vapor deposition

Silicon nitride films were deposited at low temperatures (245–370 °C) and high deposition rates (500–1700 A/min) by hot filament assisted chemical vapor deposition (HFCVD). Optical properties of these amorphous silicon nitride thin films have been extensively characterized by absorption, photoluminescence (PL), photoluminescence excitation, and electroluminescence measurements. The optical band gap of the films was varied between 2.43 and 4.74 eV by adjusting the flow rate of the disilane source gas. Three broad peaks at 1.8, 2.4, and 3.0 eV were observed in the PL spectra from these films. A simple qualitative model based on nitrogen and silicon dangling bonds adequately explains the observed PL features. The photoluminescence intensity observed in these films was 8–10 times stronger than films deposited by plasma enhanced chemical vapor deposition, under similar conditions. The high deposition rates obtained by HFCVD is believed to introduce a large number of these optically active defects.

Multiple scattering and nonlinear thermal emission of yb3+, Er3+:Y2O3 nanopowders

Radiation transport and multiple scattering calculations are presented and compared with experimental observations to characterize light attenuation in high emissivity nanopowders irradiated with low power laser light at room temperature, and to explain the associated white light emission and the onset of melting. Using radiation tuned to an absorption resonance of Yb3+ dopants in Y2O3 nanopowder, we observed the onset of intense blackbody emission above a well-defined intensity threshold. Local melting of the compact above threshold leads to the formation of single crystal microtubes. Evidence is provided to show that two-flux transport theory and diffusion theory both significantly underestimate the absorption due to dependent, multiple scattering and that the threshold for the thermal runaway process responsible for this behavior is very sensitive to porosity of the random medium.

Avalanche upconversion in Tm:YALO 3

We report the sudden appearance of upconversion fluorescence and resonant increasing absorption above a threshold intensity in Tm YALO3 at room temperature. These effects are shown to arise from nonlinear, cooperative, excited-state dynamics. Comparison with quantum theory reveals essential roles both for pairwise cross relaxation and excitation migration among Tm impurity ions.

Synthesis and Photophysical Properties of Stilbeneoctasilsesquioxanes. Emission Behavior Coupled with Theoretical Modeling Studies Suggest a 3-D Excited State Involving the Silica Core

A set of stilbene-substituted octasilicates [p-RStil(x)Ph(8-x)SiO(1.5)](8) (R = H, Me, MeO, Cl, NMe(2) and x = 5.3-8) and [o-MeStilSiO(1.5)](8) were prepared. Model compounds were also prepared including the corner and half cages: [p-MeStilSi(OEt)(3)], [p-Me(2)NStilSi(OSiMe(3))(3)], and [p-Me(2)NStilSi(O)(OSiMe)](4). These compounds were characterized by MALDI-TOF, TGA, FTIR, and (1)H NMR techniques. Their photophysical properties were characterized by UV-vis, two-photon absorption, and cathodoluminescence spectroscopy (on solid powders), including studies on the effects of solvent polarity and changes in concentration. These molecules are typically soluble, easily purified, and robust, showing T(d(5%)) > 400 degrees C in air. The full and partial cages all show UV-vis absorption spectra (in THF) identical to the spectrum of trans-stilbene, except for [o-MeStilSiO(1.5)](8), which exhibits an absorption spectrum blue-shifted from trans-stilbene. However, the partial cages show emissions that are red-shifted by approximately 20 nm, as found for stilbene-siloxane macrocycles, suggesting some interaction of the silicon center(s) with the stilbene pi* orbital in both the corner and half cages. In contrast, the emission spectra of the full cages show red-shifts of 60-100 nm. These large red-shifts are supported by density functional theoretical calculations and proposed to result from interactions of the stilbene pi* orbitals with a LUMO centered within the cage that has 4A(1) symmetry and involves contributions from all Si and oxygen atoms and the organic substituents. Given that this LUMO has 3-D symmetry, it appears that all of the stilbene units interact in the excited state, consistent with theoretical results, which show an increased red-shift with an increase in the functionalization of a single corner to functionalization of all eight corners with stilbene. In the case of the Me(2)N- derivatives, this interaction is primarily a charge-transfer interaction, as witnessed by the influence of solvent polarity on the emission behavior. More importantly, the two-photon absorption behavior is 2-3 times greater on a per p-Me(2)Nstilbene basis for the full cage than for the corner or half cages. Similar observations were made for p-NH(2)stilbenevinyl(8)OS cages, where the greater conjugation lengths led to even greater red-shifts (120 nm) and two-photon absorption cross sections. Cathodoluminescence studies done on [p-MeStilSiO(1.5)](8) or [p-MeStilOS](8) powders exhibit essentially the same emissions as seen in solution at high dilution. Given that only the emissions are greatly red-shifted in these molecules, whereas the ground-state UV-vis absorptions are not changed from trans-stilbene, except for the ortho derivative, which is blue-shifted 10 nm. It appears that the interactions are only in the excited state. Theoretical results show that the HOMO and LUMO states are always the pi and pi* states on the stilbene, which show very weak shifts with increasing degrees of functionalization, consistent with the small changes in the UV-vis spectra. The band gap between the lowest unoccupied 4a1 symmetry core state localized inside the silsesquioxane cage and the highest occupied state (pi state on stilbene), however, is markedly decreased as the number of stilbene functional groups is increased. This is consistent with the significant red-shifts in the emission spectra. The results suggest that the emission occurs from the 4a1 state localized on the cage. Moreover, for the compounds [p-RStil(6-7)Ph(2-1)OS](8), the emissions are blue-shifted compared to those of the fully substituted compounds, suggesting the molecular symmetry is reduced (from cubic), thereby reducing the potential for 3-D delocalization and raising the energy of the LUMO. The implications are that these octafunctional molecules exhibit some form of 3-D interaction in the excited state that might permit their use as molecular transistors as well as for energy collection and dispersion as molecular antennas, for example, and for nonlinear optical applications.

Observation of near‐band‐gap luminescence from boron nitride films

We report results from cathodoluminescence spectroscopy of boron nitride films grown on Si(100) substrates by ion‐source‐assisted magnetron sputtering of a hexagonal BN target. Three main peaks are observed in the near‐band‐gap region for hexagonal boron nitride films at energies of 4.90, 5.31, and 5.50 eV. We also report deep‐level emission spectra of predominantly cubic boron nitride films which are correlated with sample growth conditions. In particular we show that the emission intensity, position, and linewidth are strongly dependent on the substrate bias voltage used during sample growth.

COOPERATIVE OPTICAL BISTABILITY IN THE DIMER SYSTEM CS3Y2BR9:10% YB3+

In single crystals of the dimer compound Cs3Y2Br9:10% Yb3+ below 31 K, both visible (VIS) and near‐infrared (NIR) luminescence intensities were found to exhibit hysteresis as a function of incident NIR intensity and temperature. The optical bistability is intrinsic to Cs3Y2Br9:10% Yb3+ and not a result of an external feedback. Lowering the temperature to 11 K strongly enhances the all‐optical switching behavior. The switching on VIS cooperative upconversion and NIR luminescence transitions occurs simultaneously and with opposite polarity reflecting the competition of both emission processes. On/Off switching ratios of up to 4.8 and 1.7 were observed for VIS and NIR luminescence intensities. Using NIR luminescence spectroscopy, differences in the internal sample temperature of up to 7 K were found between the upper and lower branches of the hystereses. A two‐level density‐matrix model is developed which includes ground‐ and excited‐state interactions and shows that the intrinsic bistability due to a local ...

Continuous-wave ultraviolet laser action in strongly scattering Nd-doped alumina

We report electrically pumped, cw laser action near 405 nm from Nd(3+) -doped delta -alumina nanopowders. To our knowledge, this is the first report of stimulated emission from the high-lying F(2) -excited states, achieved through feedback from strong elastic scattering of light over transport path lengths shorter than half a wavelength.

Photoluminescence investigation of GaN films grown by metalorganic chemical vapor deposition on (100) GaAs

GaN films were grown on (100) GaAs substrates by metalorganic chemical vapor deposition and were found to be of (200) cubic or (111) cubic/(0002) hexagonal phase. Their photoluminescence characteristics remained invariant with material phase. We report assignment of band‐edge photoluminescence near 3.36 eV and 3.15–3.31 eV in apparently cubic GaN to intrinsic/bound excitons and phonon‐assisted, donor‐acceptor pair recombination respectively, on the basis of observed temperature and intensity dependences. A free exciton energy of 3.375 eV is deduced at 6.5 K.

Continuous-wave, pair-pumped laser

We report room-temperature operation of what we believe is the first continuous-wave laser that relies exclusively on cooperative upconversion by coupled ion pairs to achieve population inversion.

Origin of persistent hole burning of N-V centers in diamond

New satellite features and antiholes in the persistent hole-burning spectrum of N–V centers in diamond, as well as their dependences on applied electric fields and frequency within the inhomogeneous absorption line, are reported. These results, together with reassignments of spin states of this center, permit an understanding of the origin of the satellite holes as well as of possible mechanisms for the persistent hole-burning phenomenon itself. In addition we report narrow optical interference fringes in heterodyne-detected spectra of persistent spectral holes in the N–V defect center in diamond and discuss a recent suggestion for high-resolution Ramsey-fringe hole-burning spectroscopy of solids based on phase-separated fields.