Computational studies of the optical emission of silicon nanocrystals

We have computed absorption and emission energies of silicon nanocrystals as a function of size and of surface passivants, using both density functional theory and quantum Monte Carlo calculations. We have found that the ionic rearrangements and electronic relaxations occurring upon absorption and emission are extremely sensitive to surface chemistry. In particular, nanoclusters with similar sizes and similar absorption gaps can exhibit strikingly different emission energies. Our results provide a unifying interpretation of several recent measurements, which have observed significantly different emission energies from clusters with similar sizes. Our calculations also show that a combination of absorption and emission measurements can provide a powerful tool for identifying both the size and the surface passivants of semiconductor nanocrystals.     

On the mechanism of the emission of high-energy electrons from the surfaces of freshly peeled films: Polytetrafluoroethylene

This paper describes the results of an investigation of high-electron emission accompanying the mechanical disruption of adhesive contact in vacuo. Investigations of such emission parameters as the energy of the electrons, their angular distribution, depth of the electron capture center levels on freshly formed polymer surfaces responsible for the emission as well as the establishment of relations governing the time variation of the parameters of the emitted electrons' flux, their relation to the polymer film surface charge, and finally the numerical computations based on these experiments have led the authors to the conclusion that the mechanism of electron emission from freshly formed polymer film surfaces has a field-emission nature proceeding from surface states and is described accurately enough by the analytical expressions derived from the above considerations.     

The effects of oxygen on the detection of mercury using laser-induced breakdown spectroscopy

A systematic study of the processes associated with mercury atomic emission in a laser-induced plasma and the interactions of mercury with oxygen species is presented. At early plasma decay times, on the order of 5–10 μs, no significant variation in mercury atomic emission was observed with the addition of oxygen-containing species. At intermediate and long decay times (10–100 μs), a significant reduction in the 253.7-nm mercury emission intensity was recorded with the introduction of oxygen-containing species. The decrease in mercury emission was temporally coincident with the recombination of atomic oxygen, as measured by the O(I) emission. The decreased mercury emission was not due to thermal effects, based on plasma temperature measurements, and was independent of the molecular source of oxygen, for similar concentrations of oxygen as air, carbon dioxide, and carbon monoxide. Analysis of additional mercury atomic emission lines revealed that the reduction in mercury emission in the presence of oxygen species is limited primarily to the 253.7-nm transition. In concert, the data lead to the conclusion that the 253.7-nm mercury emission line is selectively quenched by oxygen species, primarily O₂ and NO, that are formed during the plasma recombination process. Implications for laser-induced breakdown spectroscopy-based emissions monitoring of mercury species are discussed.     

Interplay between the keto defect and the interchain interaction on the green emission of fluorene-based polymer

To investigate the interplay between on-chain keto defect and interchain interaction and its consequence on the blue emission of polyfluorene (PF), first- to third-generation dendronized PFs as well as single-fluorenone-unit doped PF (PFN), synthesized by Suzuki polycondensation, were used as model compounds for steady-state and picosecond time-resolved photoluminescence (PL) spectroscopic studies. For PF film, the broad-band green emission did not appear, although severe interchain interaction was observed. For PFN film, the green emission that peaked at approximately 540 nm decayed in a multiphasic manner, suggesting significant heterogeneity in the excitation migration toward the keto center. To further examine the interplay effect, a series of novel dendronized-PF/PFN blend films in a molar ratio of 40:1 fluorene-to-fluorenone unit were studied. With reference to pure PFN film, those of the green emission of the blends showed strong dependence on the order of dendronization, that is, a higher generation resulted in a shorter-lived green emission. These observations are discussed in terms of interchain and/or intersegment interactions between the fluorene segments and the keto defect. It is concluded that the keto unit and the keto-centered, interchain aggregation lead to severe color degradation in a synergistic manner, and that dendronization can effectively minimize the undesirable green emission.     

Microwave plasma in argon produced by a surface wave: study of the effect of pressure on the optical emission and the potentials for analysis of gaseous samples

The possibility of chemical analysis of gaseous samples by optical emission spectroscopy has been evaluated using a microwave induced plasma created by a surface wave at 210 MHz. Methane has been introduced at low concentration (1–20 ppm) in argon gas. The emission of excited CH, CN, C₂ at atmospheric pressure, was observed along the discharge and studied as a function of the methane concentration. The influence of the pressure on CH emission is presented from 10 Torr to atmospheric pressure. Contrary to usual predictions, the emission of CH bands is maximum at about 100 Torr and not at atmospheric pressure.     

Vibrational emission analysis of the CN molecules in laser-induced breakdown spectroscopy of organic compounds

Laser-induced breakdown spectroscopy (LIBS) of organic materials is based on the analysis of atomic and ionic emission lines and on a few molecular bands, the most important being the CN violet system and the C₂ Swan system. This paper is focused in molecular emission of LIBS plasmas based on the CN (B²Σ–X²Σ) band, one of the strongest emissions appearing in all carbon materials when analyzed in air atmosphere. An analysis of this band with sufficient spectral resolution provides a great deal of information on the molecule, which has revealed that valuable information can be obtained from the plume chemistry and dynamics affecting the excitation mechanisms of the molecules. The vibrational emission of this molecular band has been investigated to establish the dependence of this emission on the molecular structure of the materials. The paper shows that excitation/emission phenomena of molecular species observed in the plume depend strongly on the time interval selected and on the irradiance deposited on the sample surface. Precise time resolved LIBS measurements are needed for the observation of distinctive CN emission. For the organic compounds studied, larger differences in the behavior of the vibrational emission occur at early stages after plasma ignition. Since molecular emission is generally more complex than that involving atomic emission, local plasma conditions as well as plume chemistry may induce changes in vibrational emission of molecules. As a consequence, alterations in the distribution of the emissions occur in terms of relative intensities, being sensitive to the molecular structure of every single material.     

Factors affecting the formation of the radiation pre-peak at the operation of a Grimm-type source in pulsed DC mode

The plasma emission pre-peaks of many atomic and ionic spectral lines of Cu and Ar were systematically investigated in a Grimm-type pulsed glow discharge (PGD). To register the pre-peaks with sufficient time resolution, a monochromator with photomultiplier detection was used. When the applied power exceeded a specific threshold, pre-peaks were found in all spectral lines investigated, and it was revealed that the electrical pre-peak was the cause of the atomic emission pre-peak. The form and intensity of the pre-peak radiation were, however, found to be different for different atomic emission lines. The excitation energy of the upper energy level of the atomic line transition, and factors related to recombination and self-absorption, were found to affect the emission pre-peak. Pre-peaks observed when using pulsed DC and pulsed radio-frequency power were compared. This investigation provides insight into best practice when selecting spectral lines most suitable for analytical spectrometry using PGD.     

Isomers in the excited state of electron-transferring flavoprotein from Megasphaera elsdenii: spectral resolution from the time-resolved fluorescence spectra

Electron-transferring flavoprotein (Holo-ETF) from Megasphaera elsdenii contains two FAD's, one of which easily dissociates to form Iso-ETF (contains one FAD). Time-resolved fluorescence of FAD in Iso-ETF, and Holo-ETF were measured at 5 degrees C and 25 degrees C. Wavelength-dependent fluorescence decays of the both ETF at 5 degrees C and 25 degrees C were analyzed to resolve them into two independent spectra. It was found that Iso-ETF displayed two spectra with lifetime of 0.605 ns (emission peak, 508 nm) and with lifetime of 1.70 ns (emission peak, 540 nm) at 5 degrees C, and with lifetime of 0.693 ns (emission peak, 508 nm) and with lifetime of 2.75 ns (emission peak, 540 nm) at 25 degrees C. Holo-ETF displayed two spectra with lifetime of 0.739 ns (emission peak, 508 nm) and with lifetime of 2.06 ns (emission peak, 545 nm) at 5 degrees C, and with lifetime of 0.711 ns (emission peak, 527 nm) and with lifetime of 3.08 ns (emission peak, 540 nm) at 25 degrees C. Thus fluorescence lifetimes of every spectrum increased upon elevating temperature. Emission peaks Iso-ETF did not change much upon elevating temperature. Activation enthalpy changes, activation entropy changes and activation Gibbs energy changes of quenching rates all displayed negative. Two emission species in the both ETF may be hydrogen-bonding isomers, because isoalloxazine ring of FAD contains four hydrogen acceptors and one donor.     

Optical Diagnostics of the Effect of Oxygen on Bi-Level Contact Etch

The effect of oxygen flow rate on bi-level contact etch was studied by observing uv-visible emission from the plasma, during CHF₃/CO/O₂ etching of di-electric layers consisting of SiO₂ and SiN_x. The emission intensity of CN at 387 nm drifted progressively from wafer to wafer during plasma etch. Such a phenomenon became more obvious when using low or high oxygen flow rate, whereas for intermediate flow rates, no significant drift of emission intensity was observed. The critical dimension (CD) bias of each wafer showed a strong correlation with CN emission intensity. Possible mechanisms for such an intensity drift phenomenon are proposed. The drift of emission intensity indicates that the contribution of chamber wall polymers in wafer etching is non-negligible. The CN emission intensity is an indication of the magnitude of etching rate. Our results suggest that the variation of plasma emission intensity might be used as an index for in-line monitoring of CD bias fluctuation.     

Effect of cyclodextrin nanocavity confinement on the photorelaxation of the cardiotonic drug milrinone

We report on steady-state UV-visible absorption, emission, and picosecond emission studies of milrinone (MIR) drug in neutral water and complexed to cyclodextrins (alpha-, beta-, gamma-CD and dimethyl-beta-CD (DM-beta-CD)). The results reveal that MIR forms a 1:1 inclusion complex with CD. Upon encapsulation the emission intensity increases and the fluorescence lifetime changes from approximately 65 ps to 240-350 ps, indicating a confinement effect of the nanocages on the photophysical behavior of the drug. Due to its methyl groups, the DM-beta-CD complex shows the largest effect. The time-anisotropy experiments support the formation of 1:1 inclusion complexes and indicate motion of the drug inside the nanocavity. Furthermore, results of PM3 calculations combined with spectral and dynamical data show that the drug is not fully embedded into the cavities, and the conformation of the included complex explains the relatively short lifetimes and low emission quantum yields of these entities.     

Study of the substituent groups effect on the room-temperature phosphorescent emission of fluorene derivatives in solution

We present here the first study of the effect of substituent groups and the chemical structure of fluorene derivatives on phosphorescent emission. A group of fluorene derivatives have been studied with a new methodology of room-temperature phosphorescence emission called heavy atom induced room-temperature phosphorescence (HAI-RTP). This methodology makes use of RTP emission directly from the compound in fluid solution, without a protective medium but only with the presence of high concentrations of heavy atom perturbers and an oxygen scavenger. These experimental conditions permit sufficient interaction between the perturbers and the phosphors to produce effective population of the triplet states of the latter and, consequently, intense phosphorescent emission. Good deoxygenation conditions are obtained using sodium sulfite as the oxygen scavenger. We show here that it is possible that many fluorene derivatives can exhibit RTP emission in aqueous solutions in the absence of a protective medium. Phosphorescence spectral characteristics of these compounds (excitation and emission wavelengths and lifetime) and the optimization of the chemical variables involved in the phosphorescence phenomenon are reported. Under optimal experimental conditions, calibration graphs and detection and quantification limits in the ng ml⁻¹ level have been established.     

Trifluoroethanol as a solvent for discriminating the fluorescence of polynuclear aza-aromatic compounds from that of the parent hydrocarbon

Trifluoroethanol (TFE) is strongly hydrogen bonded to aromatic compounds containing a pyridinic nitrogen. For many aza-aromatic compounds this causes an increase in the fluorescence emission yield of up to two orders of magnitude and a change in the nature of the emission with respect to that observed in most common aliphatic alcohols. The emission from these aza-aromatic compounds in TFE is, in fact, a cation-like fluorescence. This allows the easy identification of the single components of a mixture of aromatic and aza-aromatic compounds.     

微波硫灯发射光谱的理论模拟

通过实验观测了微波硫灯的发光光谱. 利用从头计算的多组态准简并微扰理论方法, 采用cc-pVQZ基组计算了S2分子B3Σu--X3Σg-态和B″3Πu-X3Σg-态的跃迁矩及其振动态之间跃迁的弗兰克-康登因子, 导出了S2分子振动分辨发射谱. 同时, 利用含时密度泛函方法计算了Sn(n=2~8)分子的吸收谱. 将计算得到的S2分子振动分辨发射谱与实验所测得的光谱分布进行了比较分析, 解释了微波硫灯的宽谱区发光光谱的特性.     

基于电子结构理论的能量转移速率计算

以高精度的完全活化空间自洽场及二级微扰能量校正(CASPT2//CASSCF)电子结构计算为基础, 利用Förster和Dexter 2种模型, 建立了能量转移速率的数值模拟方案, 并将其用于2种典型的有机发光二极管发光分子Pt-4和FPt的光物理过程的计算, 结果发现, 蓝光态到红光态的能量转移和蓝光态到基态的辐射跃迁之间的竞争决定了发光颜色的浓度依赖性, 阐明了2个配合物溶液体系发射白光的微观机制. 通过比较2个配合物单体和双体不同电子态的结构和性质的差异, 对发光颜色与溶液浓度依赖性的微观本质给出了新的理论. 此外, 本文建立的能量转移速率模拟方案, 同时适用于其它激发态电子结构方法, 因此具有普适性.     

Continuous modification of upconversion luminescence of fluorescent dye in the crystalline colloidal arrays

The crystalline colloidal arrays with controllable photonic bandgaps were prepared by the change of volume fraction of the polystyrene microspheres. Upconversion emission property of fluorescent dye has investigated in crystalline colloidal array, and continuous modification of the upconversion emission of fluorescent dye was observed. A significant suppression of upconversion emission of dye in the range of the photonic bandgap as well as enhancement at the bandgap edge was obtained in the crystalline colloidal arrays. In addition, upconversion emission of dye was also enhanced when the excited light overlapped with the long or short bandgap edge of the crystalline colloidal arrays, which is due to slow photons effect near the edges of a photonic bandgap. The continuous modification and enhancement of upconversion emission may be important for the development of low-threshold upconversion lasers and displays.     

Influence of the alkyl side chain length on the room-temperature phosphorescence of organic copolymers

Pure organic room-temperature phosphorescence(RTP) materials have attracted wide attention owing to their excellent luminescent properties and great potential in various applications. In this work, iminostilbene and its analogues are applied to realize RTP emission by copolymerizing with acrylamide. It can be concluded that the growth of alkane chain in monomers can enhance the lifetime and photoluminescence quantum yield of RTP emission, and polymers with the larger conjugated structure of the ...     

An investigation into the role of metastable argon atoms in the afterglow plasma of a low pressure discharge

An investigation into the behaviour of metastable argon atoms in a low pressure (250 Pa) pulsed electrical discharge was undertaken in an effort to find the cause of the persisting emission from sputtered metal atoms in the afterglow of an atomic fluorimeter. Results obtained by time-resolved emission and absorption measurements of several argon and copper spectral lines indicate that low energy electrons in the afterglow are converted to high energy electrons via the recombination of electrons with argon ions and the subsequent collisions of pairs of metastable argon atoms. The high energy electrons excite the sputtered metal atoms to give rise to a slow decaying emission tail in the afterglow. A probable change in the electron energy distribution in the afterglow may also have an effect on the observed emission. This phenomenon may be reduced by the use of a suitable quenching gas.     

Semiclassical approach to collision-induced emission in the presence of intense laser radiation: An aspect in the study of cooperative chemical and optical pumping

Collion-induced emission in molecular systems in an intense laser field is studied using the semiclassical approach, with a view towards cooperative chemical and optical pumping in laser production. The formalism is developed with the electronic-field representation, which treats collision and radiative interaction on the same footing. Electronic-field surfaces can be regarded as forming spectra for spontaneous emission; and particular emission events can be accounted for by propagating classical trajectories on emission electronic-field surfaces. Pre-emission loss from the excited state is dealt with by propagating classical trajectories on a loss surface along a complex contour of emission branch points. This loss surface is derived on the basis of localized radiative couplings between electronic-field states and provides a framework to treat the general problem of discrete state-continuum interactions. The formalism is applied to a two-state, collinear exponential model to compute S-matrix elements and transition probabilities between asymptotic states.     

Role of nonemissive quenchers for the green emission in polyfluorene

The stability of fluorene-based compounds and polymers, especially at the bridged C-9 position under photoirradiation and thermal treatment, has claimed much attention. The emission of fluorenone formed by degradation of the 9-site is regarded as the origin of the low emission band at 2.2-2.3 eV in polyfluorene-based conjugated materials. We have investigated the role of nonemissive quenchers such as alkyl ketones, which were also one of the products of polyfluorene degradation, for the low-energy emission in polyfluorenes. The spectral characteristics of a blend system of polyfluorene/nonemissive quencher/fluorenone are found to accord well with the kinetics of actual polyfluorene degradation. Our results indicate that strong green emission in degraded polyfluorene would be not caused only by fluorenone, but also by nonemissive quenchers for their effectively quenching bulk emission.     

Switching the emission of di(4-ethoxyphenyl)dibenzofulvene among multiple colors in the solid state

Luminescent materials exhibiting emission switching in the solid state have drawn much attention though there is still no clear design strategy for such materials. In this letter, we reported the crystallization induced emission enhancement (CIEE) of di(4-ethoxyphenyl)dibenzofulvene (1), and achieved switching its emission among four different colors through modulation of its molecular packing patterns. We have investigated its potential application as optical recording materials. The twisted conformations of CIEE compounds afford morphology dependent emission and facilitate tuning their emission through modulation of molecular packing patterns. Thus we provide a possible design strategy for solid stimulus responsive luminescent materials.