Resolved Emission Spectra Research Articles

Vibration‐Dependent Dual‐Phosphorescent Cu4 Nanocluster with Remarkable Piezochromic Behavior

AbstractThe dual emission (DE) characteristics of atomically precise copper nanoclusters (Cu NCs) are of significant theoretical and practical interest. Despite this, the underlying mechanism driving DE in Cu NCs remains elusive, primarily due to the complexities of excited state processes. Herein, a novel [Cu4(PPh3)4(C≡C−p−NH2C6H4)3]PF6 (Cu4) NC, shielded by alkynyl and exhibiting DE, was synthesized. Hydrostatic pressure was applied to Cu4, for the first time, to investigate the mechanism of DE. With increasing pressure, the higher‐energy emission peak of Cu4 gradually disappeared, leaving the lower‐energy emission peak as the dominant emission. Additionally, the Cu4 crystal exhibited notable piezochromism transitioning from cyan to orange. Angle‐dispersive synchrotron X‐ray diffraction results revealed that the reduced inter‐cluster distances under pressure brought the peripheral ligands closer, leading to the formation of new C−H⋅⋅⋅N and N−H⋅⋅⋅N hydrogen bonds in Cu4. It is proposed that these strengthened hydrogen bond interactions limit the ligands′ vibration, resulting in the vanishing of the higher‐energy peak. In situ high‐pressure Raman and vibrationally resolved emission spectra demonstrated that the benzene ring C=C stretching vibration is the structural source of the DE in Cu4.

Vibration-Dependent Dual-Phosphorescent Cu4 Nanocluster with Remarkable Piezochromic Behavior.

The dual emission (DE) characteristics of atomically precise copper nanoclusters (Cu NCs) are of significant theoretical and practical interest. Despite this, the underlying mechanism driving DE in Cu NCs remains elusive, primarily due to the complexities of excited state processes. Herein, a novel [Cu4(PPh3)4(C≡C-p-NH2C6H4)3]PF6 (Cu4) NC, shielded by alkynyl and exhibiting DE, was synthesized. Hydrostatic pressure was applied to Cu4, for the first time, to investigate the mechanism of DE. With increasing pressure, the higher-energy emission peak of Cu4 gradually disappeared, leaving the lower-energy emission peak as the dominant emission. Additionally, the Cu4 crystal exhibited notable piezochromism transitioning from cyan to orange. Angle-dispersive synchrotron X-ray diffraction results revealed that the reduced inter-cluster distances under pressure brought the peripheral ligands closer, leading to the formation of new C-H⋅⋅⋅N and N-H⋅⋅⋅N hydrogen bonds in Cu4. It is proposed that these strengthened hydrogen bond interactions limit the ligands' vibration, resulting in the vanishing of the higher-energy peak. In situ high-pressure Raman and vibrationally resolved emission spectra demonstrated that the benzene ring C=C stretching vibration is the structural source of the DE in Cu4.

Plasma dynamics and chlorine emission characteristics on cement pastes using collinear dual-pulse laser-induced breakdown spectroscopy

The ingress of chloride can lead to the pitting corrosion of rebars, causing severe damage to concrete structures during service. Laser-induced breakdown spectroscopy (LIBS) has been demonstrated as an in-situ and reliable technique that can present cement distribution in concrete profiles, where the chlorine concentration is severely limited in the China standard. Dual-pulse LIBS has frequently been reported to enhance plasma emission. The evolution of the induced plasma generated from cement pastes is studied using an optical diagnostic system coupled with fast photography, shadowgraph, and optical emission spectroscopy, which can simultaneously record time-resolved physical information, including plasma morphology, shockwave propagation, and spatially resolved emission spectra in both single-pulse and dual-pulse configurations. The transition of the action mechanism of the second laser pulse from “initial plasma reheating” to “ablation enhancement” is demonstrated, which is responsible for the change in the plasma morphology from hemispherical to umbrella-shaped. It is observed that the new shockwave formed inside the initial shockwave is produced by the secondary ablation, which propagates faster, and shockwave fusion occurs when it approaches the initial shockwave. The spatially resolved Cl I emission at 837.59 nm is acquired, and the signal-to-background ratio (SBR) closely follows the profile of plasma temperature. The maximum SBR (> 3.0) can be accessed in the region where the plasma temperature reaches its peak (> 9200 K). Under the excitation of dual pulse with an inter-pulse delay of 200 ns, the Cl I emission can be clearly identified in the sample with a chlorine concentration of 0.252 wt% close to the critical value (0.2 wt% in the China standard), and a calibration curve is constructed with limit of detection (LOD) estimated to be 1930 ppm (dual pulse) versus 2550 ppm (single pulse).

Radial dependence diagnosis of inductively coupled Ar plasma based upon optical emission spectroscopic measurement with spectral reflectance compensation

This study proposed a simple method to evaluate the spectral reflectance of the inner wall of a vacuum chamber. A method for calculating spectral emission coefficients by taking the spectral reflectance of the chamber inner wall into account was proposed. Furthermore, plasma diagnosis based on optical emission spectroscopic (OES) measurement was performed so as to obtain radial dependence of electron temperature Te and density Ne of a radio frequency inductively coupled Argon (Ar) plasma by applying a collisional-radiative model to radially resolved emission spectra of the Ar plasma assuming axial symmetry. In addition, Langmuir probe measurement and electromagnetic simulation were performed and compared with the OES-based plasma diagnosis results. The spectral radiance compensation improved the diagnostic result by 0.6% and 3.1% for Te and Ne, respectively.

Spectral electron energy map of electron impact induced emission of nitrogen

The processes of electron impact induced fluorescence of nitrogen were studied in the electron energy range from 6 to 100 eV and in the spectral range from 330 to 1030 nm. Using the new CCD camera a Spectral Electron Energy Map of N2 was obtained. This type of data for such a wide spectral and energy range are published for the first time. The most intensive molecular emission bands were neutral nitrogen First positive system N2 (B3Πg − A3∑u+) and Second positive system N2 (C3Πu − B3Πg), First negative system N2+ (B2∑u+ − X2∑g+) and Meinel system N2+ (A2Πu − X2∑g+). The detected lower intensity transitions were Gaydon-Herman singlet system N2 (1Σu+ − a1Πg / 1Πu+ − a1Πg) and Gaydon-Green system N2 (H3Φu − G3Δg). In addition, processes of dissociative excitation and ionisation were observed, resulting in the photon emission from the neutral and singly ionised nitrogen atoms. The provided Spectral Electron Energy Map allows extraction of (i) electron energy resolved emission spectra of N2 and determination of the absolute values of excitation-emission cross sections, (ii) excitation-emission functions for any of the molecular bands or atomic lines present in the spectra.Graphic Abstract

Modeling Luminescence Spectrum of BaZrO3:Ti Including Vibronic Coupling from First Principles Calculations.

Herein, we present a methodology based on constrained density functional theory and vibrational mode computations to simulate and interpret the luminescence spectra of periodic solids. A multi-dimension harmonic model is used to combine electronic and vibrational contributions into an overall vibrationally resolved emission spectrum. We applied it to Ti-doped BaZrO3 to accurately reproduce its blue luminescence and unambiguously assign the observed luminescence to a Ti3+ + O- → Ti4+ + O2- charge transfer.

Rhenium(I) Complexes with Neutral Monodentate Coligands and Monoanionic 2-(1,2,4-Triazol-5-yl)pyridine-Based Chelators as Bidentate Luminophores with Tunable Color and Photosensitized Generation of 1O2: An Integrated Case Study Involving Photophysics and Theory.

In this work, we describe the synthesis as well as structural, photophysical, and theoretical investigation of a new coordination chemical concept involving rhenium(I) complexes bearing monoanionic 1,2,4-triazolylpyridine-based bidentate chromophores. The X-ray diffractometric analysis of single crystals revealed particular packing features: the trifluoromethylated exemplar displayed two kinds of arrangements of the coordination centers, where the bidentate ligands at the edges of the unit cell are staggered parallel to each other, whereas those inside show antiparallel stacking with respect to the external ligands. On the other hand, the complexes bearing an adamantyl substituent yield a linear arrangement, where the bulky moiety of one luminophore points to the pyridine center of the adjacent ligand of the neighboring complex while including methanol molecules hydrogen-bonded to the triazolato unit. We observed that the photophysical properties of the complexes (photoexcited-state lifetimes, photoluminescence maxima and quantum yields) can be adjusted by tuning of the substitution pattern at the bidentate luminophore as well as by variation of the monodentate coligand. The photoluminescence spectra and photoexcited-state lifetimes of the crystalline phases were measured by phosphorescence lifetime micro(spectro)scopy. Interestingly, the vibrationally resolved emission spectra of the crystals closely resemble those of diluted frozen glassy matrixes at 77 K, in contrast with the broad bands observed in amorphous solids and in fluid solutions, where the charge-transfer character is enhanced. While the photoluminescence quantum yields (ΦL) reach up to 15%, the complexes are able to attain up to 55% efficiency regarding the photosensitization of 1O2 (ΦΔ), depending on the combination of luminophore and coligand. Theoretical calculations showed that the photoexcited triplet (T1) state has a metal-ligand-to-ligand charge-transfer character, where promotion to the excited electronic configuration shortens the Re(I)-N bond involving the bidentate triazolylpyridine while stretching the three fac-CO-Re(I) bonds as well as the linkage to the axial monodentate coligand. The calculated vertical (Evl) and 0-0 (E(0-0)) radiative transition energies are in very good agreement with the experimental values (Eexplum).

Probing luminescence of rare earth ions in natural pink fluorites using Raman microscopes

AbstractIt is well‐known that many natural fluorite crystals contain rare earth ions. In this work, a series of pink fluorites is studied to demonstrate that the use of Raman microscopes allows to obtain high resolution emission spectra of trivalent rare earth ions. These emission spectra allow in principle to distinguish differences of the local environment related to the charge compensation necessary when the divalent Ca ion is replaced by a trivalent rare earth ion. The pink fluorites from the Alps have grown under hydrothermal conditions, which results in the incorporation of oxygen into the fluorite. In one sample from Juchlistock (Bern, Switzerland), a trigonal Eu3+‐oxygen center is clearly identified. Interestingly, a pink fluorite from China (Huanggang Mine, Inner Mongolia, China) shows a quite different emission spectrum from those of the Alps. In this sample, the emission bands have much lower relative intensity compared with the intensity of the CaF2 Raman peak, indicating a much lower content of Er3+ and Ho3+ which emit around 520–560 nm. Literature examples show that Raman measurements of differently colored fluorite crystals can also present sharp rare earth spectra. By extension, it is thus possible to observe and identify emission spectra of rare earth ions in other mineral crystals using Raman microspectroscopy and avoid misassignments of the corresponding observed Raman spectra.

Multiplex Detection of Antibiotic Residues in Milk: Application of MCR-ALS on Excitation-Emission Matrix Fluorescence (EEMF) Data Sets.

The presence of antibiotics and their metabolites in milk and dairy products is a serious concern because of their harmful effects on human health. In the current study, a novel synergistic bimetallic nanocluster with gold and silver as an emission fluorescence probe was investigated for the simultaneous determination of tetracycline (TC), ampicillin (AMP), and sulfacetamide (SAC) antibiotics in the milk samples using excitation-emission matrix fluorescence (EEMF) spectroscopy. The multivariate curve resolution-alternating least squares (MCR-ALS) method was implemented to analyze augmented EEMF data sets to quantify the multicomponent systems in the presence of interferences with considerable spectral overlap. A pseudo-univariate calibration curve of the resolved emission spectra intensity against the concentration of the mentioned antibiotics was linear in the range of 5-5000 ng mL-1 for AMP and 50-5000 ng mL-1 for TC and SAC. The calculated values of the limit of detection ranged between 1.4 and 14.6 ng mL-1 with a relative standard deviation (RSD) of less than 4.9%. The obtained results show that the EEMF/MCR-ALS methodology using an emission fluorescence probe is a powerful tool for the simultaneous quantification of TC, AMP, and SAC in complex matrices with highly overlapped spectra.

Optical Characterization of Sodium Fluorescein In Vitro and Ex Vivo.

ObjectiveThe utilization of fluorescein-guided biopsies and resection has been recently discussed as a suitable strategy to improve and expedite operative techniques for the resection of central nervous system (CNS) tumors. However, little is known about the optical properties of sodium fluorescein (NaFl) in human tumor tissue and their potential impact on ex vivo analyses involving fluorescence-based methods.MethodsTumor tissue was obtained from a study cohort of an observational study on the utilization of fluorescein-guided biopsy and resection (n=5). The optical properties of fluorescein-stained tissue were compared to the optical features of the dye in vitro and in control samples consisting of tumor tissue of high-grade glioma patients (n=3) without intravenous (i.v.) application of NaFl. The dye-exposed tumor tissues were used for optical measurements to confirm the detectability of NaFl emission ex vivo. The tissue samples were fixed in 4%PFA, immersed in 30% sucrose, embedded in Tissue-Tek OCT compound, and cut to 10 μm cryosections. Spatially resolved emission spectra from tumor samples were recorded on representative slides with a Confocal Laser Scanning Microscope FV1000 (Olympus GmbH, Hamburg, Germany) upon excitation with λexc = 488 nm.ResultsOptical measurements of fluorescein in 0.9% sodium chloride (NaCl) under in vitro conditions showed an absorption maximum of λmax abs = 479 nm as detected with spectrophotometer Specord 200 and an emission peak at λmax em = 538 nm recorded with the emCCD detection system of a custom-made microscope-based single particle setup using a 500 nm long-pass filter. Further measurements revealed pH- and concentration-dependent emission spectra of NaFl. Under ex vivo conditions, confocal laser scanning microscopy of fluorescein tumor samples revealed a slight bathochromic shift and a broadening of the emission band.ConclusionTumor uptake of NaFl leads to changes in the optical properties – a bathochromic shift and broadening of the emission band – possibly caused by the dye’s high pH sensitivity and concentration-dependent reabsorption acting as an inner filter of the dye’s emission, particularly in the short wavelength region of the emission spectrum where absorption and fluorescence overlap. Understanding the ex vivo optical properties of fluorescein is crucial for testing and validating its further applicability as an optical probe for intravital microscopy, immunofluorescence localization studies, and flow cytometry analysis.

Temporal resolved atomic emission spectroscopy on a pulsed electrolyte cathode discharge for improving the detection sensitivity of Cu

Atmospheric pressure electrolyte cathode discharge plasma presents a great potential on detecting heavy metal pollutants. In this paper, a novel microsecond pulsed electrolyte cathode discharge was generated and coupled with temporal resolved atomic emission spectra to analyze Cu element, as one of the representative heavy metals. The waveforms of voltage and current, as well as optical emission spectra of discharge were investigated, and the experimental conditions were optimized. The spatiotemporal resolved spectra of Cu I (324.8 nm), OH (A2Σ–X2Π) and N2 (C3Πu–B3Πg) were diagnosed. The spatiotemporal distributions of gas temperature and electron density were calculated by the rotational temperature of OH (A) and the Stark broadening of Hβ (486.1 nm), respectively. It was found that the optimal detection sensitivity of Cu are obtained under the conditions of HNO3 solution with 1.0 pH value, 3.0 mL/min solution flow rate, 8.5 kV pulse peak voltage, and 100 μs pulse width. The interferences of spectral line of Cu I (324.8 nm) are mainly sourced by the spectral bands of N2 (C-B) and OH (A-X), which could be reduced by the temporal resolved spectra. The limit of detection of Cu was improved from 0.217 mg/L to 0.092 mg/L by acquiring spectra only in 25–100 μs, under the optimal conditions. Furthermore, the gas temperature and electron density play important roles in the spatiotemporal evolution of discharge and the improvement of detection sensitivity for elemental analysis.

Spectral analyses of Dy3+/Sr2+: LaF3 and Dy3+/Ca2+: LaF3 mixed crystals for laser applications

Mixed crystals of Dy3+/Sr2+: LaF3 and Dy3+/Ca2+: LaF3 were grown by Bridgman technique and their spectral properties were investigated. Spectra broadening and peak shifts were observed, indicating the co-doping of Sr2+/Ca2+ brings about a more disordered local symmetry of Dy3+, which makes both crystals favorable for tunable lasing action. Low-temperature high resolution excitation and emission spectra were carried out for exploring the types of luminescent center of Dy3+ in crystals. Room-temperature absorption and emission spectra, together with the fluorescence decay curves were studied in both crystals for estimating their potentials for yellow and MIR lasers. Under 450 nm excitation, the largest emission cross-sections at 571 nm of 1.51 × 10−21 cm2 for Dy3+/Sr2+: LaF3 crystal and 1.56 × 10−21 cm2 for Dy3+/Ca2+: LaF3 crystal, along with the lifetimes of Dy3+: 4F9/2 level as 0.983 ms for Dy3+/Sr2+: LaF3 crystal, 1.143 ms for Dy3+/Ca2+: LaF3 crystal were obtained, respectively. Besides yellow emissions, MIR emissions approximately at 3 μm are more appealing. Under 1280 nm excitation, the largest emission cross-sections of 0.304 × 10−20 cm2 at 2885 nm in Dy3+/Sr2+: LaF3 crystal, and 0.319 × 10−20 cm2 at 2880 nm in Dy3+/Ca2+: LaF3 crystal, together with rather long lifetimes of Dy3+: 6H13/2 in the level of milliseconds were achieved, making them useful media for MIR lasers.

Total Emission Time Resolved Decay: a Method for Measurement and Resolution of Broad-Band Emission.

This article reports a time-resolved fluorescence data acquisition technique termed as "Total Emission Time Resolved Decay" (TETRD). TETRD is recorded by using zero-order diffraction of emission grating in TCSPC instrument. TETRD decay curve has entire wavelength dependent decay information buried in it. Cut-off filters are used to avoid scattering contamination. Two existing approaches are used for analysing the interconnected TETRD data. (i) First, global analysis: for discretely decaying multiple components, TETRD dataset is analyzed using global analysis. The normalized pre-exponentials (αi) and relative amplitudes (fi) recovered from global analysis reflect the individual component emission more faithfully and resembles with steady-state spectral data as well. (ii) Second, stretched exponential fitting (StrEF): for continuous lifetime distribution systems, StrEF (I(t) = I0 exp[-(t/τ)1/h]) has been used to analyse TETRD data. The average lifetime (τ) of StrEF matches well with the average lifetime of multi-exponential fitting, the heterogeneity factor (h) of StrEF is an additional parameter, which informs about local heterogeneity in the system. It is shown that the lifetimes obtained with TETRD matches well with the lifetimes obtained using conventional time resolved emission spectra (TRES). TETRD holds advantage in rapid data acquisition and facilitates inclusion of another variable (like concentration, solvent composition, pH, excitation wavelength etc.) into experimental design. Further, with the use of an appropriate data analysis tool, the multi-component decay profiles can be resolved conveniently.

Spectral and spatial dynamics of a multimode GaN-based blue laser diode

ABSTRACTHigh-resolution spectral analysis of a multimode GaN-based blue laser diode was performed as a function of temperature and current both below and above the threshold levels. Maps of longitudinal modes evolution as a function of current and temperature were obtained from the highly resolved emission spectra of the laser diode. The evolution of emitted longitudinal modes with current and temperature exhibited redshifts at rates of 0.0059 nm/mA and 0.0149 nm/°C, respectively. Similarly, the laser gain profile was observed to shift towards longer wavelengths but with rates of 0.022 nm/mA and 0.0439 nm/°C. The longitudinal mode spacing of 0.0540 nm was experimentally evaluated and compared with its equivalent theoretically predicted value.

Time-resolved photoluminescence study of excited states in nanostructured melanin

Time resolved emission spectra (TRES), 3D maps of photoluminescence excitation-emission (PLE maps), 3D maps of TRES, and kinetics of photoluminescence (PL) spectra of natural and synthetic melanin, as well as melanin composites with surfactant, sodium dodecyl benzenesulfonate, have been studied. The kinetics of PL and TRES for the melanin and the composites were investigated at low temperatures that allowed to discuss melanin’s intermolecular complexation, nano-aggregation and formation of charge transfer states. Particularly, the radiation of Frenkel excitons from fragments of different degrees of conjugation that are the parts of molecular nanodisks of melanin is observed. Furthermore, charge transfer excitons (CT-excitons) can be formed and observed at both room and helium temperatures. Some bands in the PL spectra of melanin, depending on temperature, behave like excimer radiation. The studies are aiming to understand the electronic properties of various melanins, particularly natural ones.

Unravelling the Mechanism of Excited-State Interligand Energy Transfer and the Engineering of Dual Emission in [Ir(C∧N)2(N∧N)]+ Complexes.

Fundamental insights into the mechanism of triplet-excited-state interligand energy transfer dynamics and the origin of dual emission for phosphorescent iridium(III) complexes are presented. The complexes [Ir(C∧N)2(N∧N)]+ (HC∧N = 2-phenylpyridine (1a-c), 2-(2,4-difluorophenyl)pyridine (2a-c), 1-benzyl-4-phenyl-1,2,3-triazole (3a-c); N∧N = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole (pytz, a), 1-benzyl-4-(pyrimidin-2-yl)-1,2,3-triazole (pymtz, b), 1-benzyl-4-(pyrazin-2-yl)-1,2,3-triazole (pyztz, c)) are phosphorescent in room-temperature fluid solutions from triplet metal-to-ligand charge transfer (3MLCT) states admixed with either ligand-centered (3LC) (1a, 2a, and 2b) or ligand-to-ligand charge transfer (3LL'CT) character (1c, 2c, and 3a-c). Particularly striking is the observation that pyrimidine-based complex 1b exhibits dual emission from both 3MLCT/3LC and 3MLCT/3LL'CT states. At 77 K, the 3MLCT/3LL'CT component is lost from the photoluminescence spectra of 1b, with emission exclusively arising from its 3MLCT/3LC state, while for 2c switching from 3MLCT/3LL'CT- to 3MLCT/3LC-based emission is observed. Femtosecond transient absorption data reveal distinct spectral signatures characteristic of the population of 3MLCT/3LC states for 1a, 2a, and 2b which persist throughout the 3 ns time frame of the experiment. These 3MLCT/3LC state signatures are apparent in the transient absorption spectra for 1c and 2c immediately following photoexcitation but rapidly evolve to yield spectral profiles characteristic of their 3MLCT/3LL'CT states. Transient data for 1b reveals intermediate behavior: the spectral features of the initially populated 3MLCT/3LC state also undergo rapid evolution, although to a lesser extent than that observed for 1c and 2c, behavior assigned to the equilibration of the 3MLCT/3LC and 3MLCT/3LL'CT states. Density functional theory (DFT) calculations enabled minima to be optimized for both 3MLCT/3LC and 3MLCT/3LL'CT states of 1a-c and 2a-c. Indeed, two distinct 3MLCT/3LC minima were optimized for 1a, 1b, 2a, and 2b distinguished by upon which of the two C∧N ligands the excited electron resides. The 3MLCT/3LC and 3MLCT/3LL'CT states for 1b are very close in energy, in excellent agreement with experimental data demonstrating dual emission. Calculated vibrationally resolved emission spectra (VRES) for the complexes are in excellent agreement with experimental data, with the overlay of spectral maxima arising from emission from the 3MLCT/3LC and 3MLCT/3LL'CT states of 1b convincingly reproducing the observed experimental spectral features. Analysis of the optimized excited-state geometries enable the key structural differences between the 3MLCT/3LC and 3MLCT/3LL'CT states of the complexes to be identified and quantified. The calculation of interconversion pathways between triplet excited states provides for the first time a through-space mechanism for a photoinduced interligand energy transfer process. Furthermore, examination of structural changes between the possible emitting triplet excited states reveals the key bond vibrations that mediate energy transfer between these states. This work therefore provides for the first time detailed mechanistic insights into the fundamental photophysical processes of this important class of complexes.

Time Evolution of Local pH Around a Photo-Acid in Water and a Polymer Hydrogel: Time Resolved Fluorescence Spectroscopy of Pyranine.

In this work, we propose a new analysis of the time resolved emission spectra of a photo-acid, HA, pyranine (8-hydroxypyrene-1,3,6-trisulphonic acid, HPTS) based on time resolved area normalized emission spectra (TRANES). Presence of an isoemissive point in TRANES confirms the presence of two emissive species (HA and A- ) inside the system in bulk water and inside a co-polymer hydrogel [F127, (PEO)100 -(PPO)70 -(PEO)100 ]. We show that following electronic excitation, the local pH around HPTS, is much lower than the bulk pH presumably because of ejection of proton from the photo-acid in the excited state. With increase in time, the local pH increases and reaches the bulk value. We further, demonstrate that the excited state pKa of HPTS may be estimated from the emission intensities of HA and A- at long time. The time constant for time evolution of pH is ∼630 ps in water, ∼1300 ps in F127 gel and ∼4700 ps in CTAB micelle. The location and local viscosity sensed by the probe is ascertained using fluorescence correlation spectroscopy (FCS) and fluorescence anisotropy decay. The different values of the local viscosity reported by these two methods are reconciled.

Phase and photoluminescence evolution of (Mg1−xBax)2SiO4: Eu phosphors

(Mg1−xBax)1.95SiO4:0.05Eu phosphors were synthesized by high temperature solid-state reaction at 1200 °C. The x-ray diffraction analysis showed the host phase changing as x value increasing could be denoted as γ-Mg2SiO4, β-Mg2SiO4 mixture (x < 0.2) → Ba2SiO4, β-Mg2SiO4, γ-Mg2SiO4 mixture (0.2 ≤ x < 0.3) → Ba2SiO4, Ba3MgSi2O8, β-Mg2SiO4 mixture (0.3 ≤ x < 0.7) → Ba2SiO4 (x ≥ 0.7). For Ba2SiO4 phase powder (Mg1−xBax)2SiO4 , x ≥ 0.7), the replacement of Mg into Ba ions could improve the crystallization, and Mg2+ ions prefer 9-coodinated Ba2+(II) ions more than 10-coodinated Ba2+(I) ions. Furthermore, there is no change in the phase when Eu ions adding. Photoluminescence spectra analysis showed that (Mg1−xBax)1.95SiO4:0.05Eu phosphors exhibited from typical Eu3+ line emission to typical Eu2+broad band emission under UV excitation, and the powder would be used as green phosphor when x ≥ 0.3. The intensity of mixture green phosphor (0.3 ≤ x < 0.7) increases as x value increases. While, the intensity of Ba2SiO4 single phase green phosphor (x ≥ 0.7) decreases as x value increases. The high resolution emission spectra of (Mg1−xBax)1.95SiO4:0.05Eu (x ≥ 0.7) analysis indicates 10-coodinated Eu2+(I) contributes more than 9-coodinated Eu2+(II) for the green emission, and bigger Eu2+(I)/Eu2+(II) ratio when more Mg2+ ions incorporating to Ba2SiO4 phase crystal. The high-resolution x-ray photoelectron spectroscopy (XPS) analysis of Eu4d showed the Eu ion valence is rarely affected by cation substitution. So the better crystalline and higher Eu2+(I)/Eu2+(II) ratio could used to explain the luminescence improvement of Ba2SiO4 phase green phosphor with Mg2+ cation substitution.

Hyperfine structure measurements of neutral atomic iodine (127I) in the infrared region (1800-6000 cm−1)

Experimental measurements of high resolution emission spectra of neutral atomic iodine (I I) have been extended to cover the mid-infrared spectral regions (1800–6000 cm−1) using Fourier transform spectroscopy. A total of 354 spectral lines are reported here in the above spectral range. While the region between 3000 and 6000 cm−1 were recorded using a conventional quartz Electrodeless Discharge lamps (EDL), spectra in the region 1800–3000 cm−1 were detected using specially prepared EDLs with a CaF2 window. Hyperfine structure analysis has been carried out on 224 spectral lines, of which 176 are reported for the first time. The magnetic dipole constant (A) and electric quadrupole constant (B) have been derived for 97 energy levels.

Combined Spatially Resolved Optical Emission Imaging and Modeling Studies of Microwave-Activated H2/Ar and H2/Kr Plasmas Operating at Powers and Pressures Relevant for Diamond Chemical Vapor Deposition.

Microwave (MW) activated H2/Ar (and H2/Kr) plasmas operating under powers and pressures relevant to diamond chemical vapor deposition have been investigated experimentally and by 2-D modeling. The experiments return spatially and wavelength resolved optical emission spectra of electronically excited H2 molecules and H and Ar(/Kr) atoms for a range of H2/noble gas mixing ratios. The self-consistent 2-D( r, z) modeling of different H2/Ar gas mixtures includes calculations of the MW electromagnetic fields, the plasma chemistry and electron kinetics, heat and species transfer and gas-surface interactions. Comparison with the trends revealed by the spatially resolved optical emission measurements and their variations with changes in process conditions help guide identification and refinement of the dominant plasma (and plasma emission) generation mechanisms and the more important Ar-H, Ar-H2, and H-H2 coupling reactions. Noble gas addition is shown to encourage radial expansion of the plasma, and thus to improve the uniformity of the H atom concentration and the gas temperature just above the substrate. Noble gas addition in the current experiments is also found to enhance (unwanted) sputtering of the copper base plate of the reactor; the experimentally observed increase in gas phase Cu* emission is shown to correlate with the near substrate ArH+ (and KrH+) ion concentrations returned by the modeling, rather than with the relatively more abundant H3+ (and H3O+) ions.