Visible upconversion emission of Pr3+ doped gadolinium gallium garnet nanocrystals

The luminescence properties of a Pr3+-doped gadolinium gallium garnet (GGG, Gd3Ga5O12) nanocrystalline host were investigated. Dominant blue/green emission was observed emanating from the 3P0 --> 3H4 transition after excitation using a wavelength of 457.9 nm. Continuous wave excitation into the 1D2 level of the Pr3+ ion at 606.9 nm transition produced blue upconversion luminescence spectra, ascribed to emission from the 3P1 --> 3H4 and 3P0 --> 3H4 transitions. The increase in the decay times of the observed transitions following excitation with 606.9 nm is indicative of the dominance of an energy transfer upconversion (ETU) mechanism relative to excited state absorption (ESA). Furthermore, blue, green and red upconversion emission was observed from the 3P0, 3P1 and 1D2 states following excitation into the 1G4 energy level with 980 nm. No change in the decay times of the emitting states was observed following excitation with a wavelength of 980 or 457.9 nm; hence, upconversion was determined to primarily occur through ESA. The luminescence properties of the nanocrystals are compared to a single crystal of GGG:Pr3+ (bulk) with an identical Pr3+ concentration (1%).     

A low-power, atmospheric pressure, pulsed plasma source for molecular emission spectrometry

A low-power, plasma source-based, portable molecular emission detector is described in this paper. The detector employs a pulsed-plasma source operated at atmospheric pressure for molecular fragmentation and excitation. The plasma was generated with a home-built high-voltage pulsed power supply. The average operational power of the detector was less than 0.2 W. The effects of operational parameters such as plasma gas, voltage, and plasma gas flow rate were investigated. Molecular emission spectra of a variety of organic compounds were studied. The features of the emission spectra obtained with the pulsed plasma source were significantly different from those obtained with direct current (dc) discharge at a power higher than 10 W. The spectra obtained in this work showed strong CH emission at 431.2 nm; however, the typical CN emission observed with a conventional dc plasma source at 383-388 nm was very weak in most cases. The strong CN emission was only obtained for compounds containing nitrogen, such as aniline. Dimethyl sulfoxide can be detected at a limit of 200 ppb using helium plasma by observing the emission band of the CH radical. The detector was very stable and did not experience electrode fouling even with the introduction of organic vapors. Such a detector is very promising for organic vapor detection.     

Experimental and simulated angular profiles of fluorescence and diffuse reflectance emission from turbid media

Given the wavelength dependence of sample optical properties and the selective sampling of surface emission angles by noncontact imaging systems, differences in angular profiles due to excitation angle and optical properties can distort relative emission intensities acquired at different wavelengths. To investigate this potentiality, angular profiles of diffuse reflectance and fluorescence emission from turbid media were evaluated experimentally and by Monte Carlo simulation for a range of incident excitation angles and sample optical properties. For emission collected within the limits of a semi-infinite excitation region, normalized angular emission profiles are symmetric, roughly Lambertian, and only weakly dependent on sample optical properties for fluorescence at all excitation angles and for diffuse reflectance at small excitation angles relative to the surface normal. Fluorescence and diffuse reflectance within the emission plane orthogonal to the oblique component of the excitation also possess this symmetric form. Diffuse reflectance within the incidence plane is biased away from the excitation source for large excitation angles. The degree of bias depends on the scattering anisotropy and albedo of the sample and results from the correlation between photon directions upon entrance and emission. Given the strong dependence of the diffuse reflectance angular emission profile shape on incident excitation angle and sample optical properties, excitation and collection geometry has the potential to induce distortions within diffuse reflectance spectra unrelated to tissue characteristics.     

Measuring scatter with a cryogenic probe and an ICCD camera: recording absorption spectra in Shpol'skii matrixes and fluorescence quantum yields in glassy solvents

Recording absorption spectra via transmittance through frozen matrixes is a challenging task. The main reason is the difficulty in overcoming the strong scattering light reaching the detector. This is particularly true when thick samples are necessary for recording absorption spectra of weak oscillators. In the case of strongly fluorescent compounds, additional errors in absorbance measurements arise from the emission reaching the detector, which might have an intensity comparable to that of the transmitted light. This article presents a fundamentally different approach to low-temperature absorption measurements as the sought for information is the intensity of laser excitation returning from the frozen sample to the ICCD. Laser excitation is collected with the aid of a cryogenic fiber optic probe. The feasibility of our approach is demonstrated with single-site and multiple-site Shpol'skii systems. The 4.2 K absorption spectra show excellent agreement with their literature counterparts recorded via transmittance with closed-cycle cryogenators. Fluorescence quantum yields measured at room temperature compare well to experimental data acquired in our laboratory via classical methodology. Similar agreement is observed between 77 K fluorescence quantum yields and previously reported data acquired with classical methodology. We then extend our approach to generate original data on fluorescence quantum yields at 4.2 K.     

Wavelength-dependent model of Kr flash lamp emission and absorption

We present a simple model of the angular intensity distribution of linear flash lamps for laser pumping application, which also takes into account the plasma column absorption during flash pulse. The model parameters are derived by single-shot measurements of plasma emission and transmission, performed with an imaging spectrometer and a CCD detector. The model consists in a linear superposition, wavelength by wavelength, of a surface (opaque) and a volume (transparent) emitter and represents a good approximation of the time-averaged lamp emission and absorption for pulse durations from 50 mus to 2 ms. This model is a suitable tool for reflector optimization of flash-lamp-pumped solid-state lasers, allowing complete wavelength-dependent ray tracing with currently available computing power. Some sample applications are also shown and discussed, with results of ray tracing for a slab laser and evaluation of the effects of lamp blackbody emission for several laser active media and flash lamp excitation pulses.     

Rapid multiexcitation fluorescence spectroscopy system for in vivo tissue diagnosis

We have designed, fabricated, and tested a compact, transportable, excitation-emission spectrofluorimeter with optical-fiber light delivery and collection for use in rapid analysis of tissues in a clinical setting. This system provides up to eleven different excitation wavelengths, permitting collection of all the corresponding emission spectra in approximately 600 ms. It uses a N(2) laser that pumps a sequence of dyes placed in cuvettes on a rotating wheel. A white-light excitation source permits acquisition of the tissue's diffuse reflectance spectrum on each cycle. Return fluorescence and reflected light are dispersed by a small spectrograph and detected by a photodiode-array detector. The system can collect a single-shot spectrum from biological tissue with a signal-to-noise ratio in excess of 50:1.     

An inductively coupled plasma carbon emission detector for aqueous carbohydrate separations by liquid chromatography

An inductively coupled plasma atomic emission spectrometer is used to detect carbon-containing compounds following separation by high-performance liquid chromatography. A calcium form ligand exchange column with distilled and deionized water as the mobile phase is used to separate carbohydrates. The eluting species are detected by monitoring the carbon atomic emission line at 193.09 nm. The mass detection limits using a photomultiplier tube for sucrose and glucose are 50 ng, while that for fructose is 60 ng. The carbon emission detector should provide the same detection limit for any compound with a similar mass percent of carbon, whether or not the compound exhibits appreciable absorption characteristics. While the carbon emission detector will universally detect any organic compound, it will discriminate against species with high molar absorptivity that may be present at low concentration. Such species may act as interferences in chromatograms generated with conventional UV-visible absorption detectors. To demonstrate the utility of the carbon emission detector, three sugars (glucose, fructose, sucrose) are determined in apple, crangrape, and orange juice.     

Unmixing coral fluorescence emission spectra and predicting new spectra under different excitation conditions

An algorithm was developed that uses prototype spectra and least-squares minimization to unmix the relative contributions of individual pigments to the composite fluorescence emission spectrum of reef corals. Field measurements indicated that it was necessary to include allowance for spectral shift of the wavelength peak of the prototype emission spectra. The unmixed spectra are used to predict the shape and amplitude of composite spectra that would be expected under different excitation conditions. We found that, for cases in which the pigments occur singly or with significant spectral separation, it is necessary to consider the properties of the excitation light sources, only, to make accurate predictions. In cases with spectral overlap the contribution of interpigment coupling cannot be neglected.     

First-principles study of silicon nanocrystals: structural and electronic properties, absorption, emission, and doping

Total energy calculations within the Density Functional Theory have been carried out in order to investigate the structural, electronic, and optical properties of un-doped and doped silicon nanostructures of different size and different surface terminations. In particular the effects induced by the creation of an electron-hole pair on the properties of hydrogenated silicon nanoclusters as a function of dimension are discussed in detail showing the strong interplay between the structural and optical properties of the system. The distortion induced on the structure by an electronic excitation of the cluster is analyzed and considered in the evaluation of the Stokes shift between absorption and emission energies. Besides we show how many-body effects crucially modify the absorption and emission spectra of the silicon nanocrystals. Starting from the hydrogenated clusters, different Si/O bonding at the cluster surface have been considered. We found that the presence of a Si--O--Si bridge bond originates significative excitonic luminescence features in the near-visible range. Concerning the doping, we consider B and P single- and co-doped Si nanoclusters. The neutral impurities formation energies are calculated and their dependence on the impurity position within the nanocrystal is discussed. In the case of co-doping the formation energy is strongly reduced, favoring this process with respect to the single doping. Moreover the band gap and the optical threshold are clearly red-shifted with respect to that of the pure crystals showing the possibility of an impurity based engineering of the absorption and luminescence properties of Si nanocrystals.     

Template-free Fabrication and Luminescent Characterization of Highly Uniform and Monodisperse Y2O2S:Sm3+ Hollow Submicrospheres

Well dispersed and homogeneous Y2O2S:Sm3+ hollow submicrospheres were successfully achieved by a templatefree solvothermal method combining with a postcalcining process.The crystalstructure and particle morphology were investigated by the X-ray diffraction(XRD),Fourier transform infrared(FT-IR) spectra,scanning and transmission electron microscopy(SEM and TEM),respectively.A possible growth mechanism was proposed to reveal the formation process.Luminescence properties of the Y2O2S:Sm3+ long-lasting phosphor were analyzed by measuring the excitation spectra,emission spectra,afterglow decay curve and thermoluminescence curve.The excitation spectra indicated that the phosphor could be excited effectively by the ultraviolet-light emitting diode(UV-LED) or blue LED,and the emission spectra showed that the phosphor could emit red light from 600 to 650 nm.     

CdTe/CdMnTe多量子阱的生长和激子复合动力学性质的研究

用分子束外延在GaAs衬底上生长了CdTe/Cd0.8Mn0.2Te多量子 结构,利用X射线衍射（XRD）、低激发密度下的PL光谱和变密度激发的ps时间分辨光谱研究了CdTe/CdMnTe多量子阱的结构和激子复合特性。在变密度激发的ps时间分辨光谱中,发现不同激发密度下发光衰减时间不同,认为它的机理可能是无辐射复合引起的。     

Exploring the possibility of early cataract diagnostics based on tryptophan fluorescence

A novel route for early cataract diagnostics is investigated based on the excitation of tryptophan fluorescence (TF) at the red edge of its absorption band at 317 nm. This allows penetration through the cornea and aqueous humour to provide excitation of the ocular lens. The steepness of the red edge gives the potential of depth control of the lens excitation. Such wavelength selection targets the population of tryptophan residues, side chains of which are exposed to the polar aqueous environment. The TF emissions around 350 nm of a series of UV-irradiated as well as control lenses were observed. TF spectra of the UV cases were red-shifted and the intensity decreased with the radiation dose. In contrast, intensity of non-tryptophan emission with maximum at 435 nm exhibited an increase suggesting photochemical conversion of the tryptophan population to 435 nm emitting molecules. We demonstrate that the ratio of intensities at 435 nm to that around 350 nm can be used as a measure of early structural changes caused by UV irradiation in the lens by comparison with images from a conventional slit-lamp, which can only detect defects of optical wavelength size. Such diagnostics at a molecular level could aid research on cataract risk investigation and possible pharmacological research as well as assisting surgical lens replacement decisions.     

Study of laser-induced breakdown emission from liquid under double-pulse excitation

The application of laser-induced breakdown spectroscopy to liquid samples, by use of a Nd:YAG laser in double-pulse excitation mode, is described. It is found that the line emission from a magnesium ion or atom is more than six times greater for double-pulse excitation than for single-pulse excitation. The effect of interpulse separation on the emission intensity of a magnesium ion and a neutral atom showed an optimum enhancement at a delay of 2.5-3 micros. The intensity of neutral atomic line emission dominates the ion emission from the plasma for higher interpulse (>10 micros) separation. A study of the temporal evolution of the line emission from the plasma shows that the background as well as line emission decays faster in double-pulse excitation than in single-pulse excitation. The enhancement in the emission seems to be dominated by an increase in the volume of the emitting gas. The limit of detection for a magnesium solution improved from 230 parts per billion (ppb) in single-pulse mode to 69 ppb in double-pulse mode.     

新型白光LED用SrMg_2(PO_4)_2单-基质荧光粉

本文通过高温固相法合成了紫外光LED用SrMg2(PO4)2为基质Eu2+,Tb3+和Mn2+为激活剂的白色荧光粉。采用XRD对荧光粉的结构和相纯度进行分析,Eu2+、Tb3+及Mn2+的加入对其结构没有明显的影响,且无杂相生成;当用Ca部分取代Sr时Eu2+和Mn2+的发射带分别发生红移和蓝移且二者之间存在着明显的能量传递;当引入共激活剂Tb3+时对其荧光光谱进行了详细研究,发现Eu2+和Tb3+,Eu2+和Mn2+之间存在部分的能量传递,通过调整它们的相对掺杂浓度可以得到发白光的荧光粉。     

Modified spontaneous emission in oligo (p-phenylene vinylene) planar microcavities

This paper reports on the photoluminescence properties of phenylene vinylene oligomers films (OPV) the emission of which was modified by microcavity effect. Films with 4 and 6 vinyl groups (respectively denoted OPV-4 and OPV-6) were investigated. A strong blue luminescence at 470 nm is observed for OPV-4. OPV-6 shows an emission spectrum quite similar to that of poly phenylene vinylene (PPV). Photoluminescence excitation measurements (PLE) give similar behaviors for the two samples and do not show any change in the shape of the spectra. Ageing under UV irradiation (380 nm) of the unencapsulated OPV-4 layers was evidenced by an exponential decrease of the photoluminescence intensity of about 40% after 3 h a continuous illumination. OPV-6 samples, aged on shelf, for weeks does only show a small decrease (15%) of the PL level over more than 7 h under continuous UV irradiation. Microcavity related effects were observed by inserting the films between two mirrors. These are generally a TiO₂/SiO₂ distributed Bragg reflectors (DBR) as bottom mirror and a Ag film as top mirror. However best results were obtained with two dielectric DBR. As expected, a strong enhancement of the emission at the cavity resonance and pronounced angular effects (emission peaking in the direction normal to the surface of the device) were observed. The importance of the position of the emitting material within the microcavity is evidenced with a thin tris(8-hydroxy) quinoline aluminum (Alq) embedded in SiO₂ with various cavity configurations.     

Light-emitting-diode-induced fluorescence detection of fluorescent dyes for capillary electrophoresis microchip with cross-polarization method

A cross-polarization scheme is presented to filter out the excitation light from the emission spectrum of fluorescent dyes using green light emitting diodes as a light source and a linear charge coupled device as an intensity detector. The excitation light was linearly polarized and was then used to illuminate the fluorescent dyes in the microchannels of a capillary electrophoresis microchip. The detector was shielded by the second polarizer, oriented perpendicular to the excitation light. The fluorescent signals from Rhodamine B dyes were measured in a dilution series with resulting emission signals and four different concentrations of fluorescent dyes were detected simultaneously with the same excitation source and detector. A limit-of-detection of 1 μM was demonstrated for Rhodamine B dye under the optimal conditions.     

Design, fabrication and performance evaluation of a 22-channel direct reading atomic emission spectrometer using inductively coupled plasma as a source of excitation

The indigenous design, fabrication and performance evaluation of a polychromator, using inductively coupled plasma (ICP) as a source of excitation, are described. A concave holographic grating is used as the dispersing element and a Paschen — Runge mount is chosen to focus the spectra over a wide range along the Rowland circle. Twenty-two exit slits, mounted along the circle, precisely correspond to the wavelengths used for determination of up to twenty elements present in the plasma. Radiations emerging from the exit slits are detected by photomultiplier tubes placed behind them. The photomultiplier signal is recorded by an electronic system consisting of an integrator and a PC-based data acquisition system. The performance of the spectrometer has been evaluated with an ICP excitation source. Synthetic standards in deionized water containing a mixture of twenty impurities have been analysed. Typical determination limits observed for elements range from sub-ppm to ppm levels. All the elements present as impurities can be detected simultaneously. It is also observed that each element has a different emitting region in the ICP flame for which the maximum signal to the background is obtained. The determination limits obtained corresponding to these zones are the lowest. A study of the sensitive emitting zones for several elements has been carried out and the results are demonstrated by photographs of the ICP flame. The study will help in achieving the minimum value of determination limit for an impurity element.     

Element-specific electronic structure of Mn dopants and ferromagnetism of (Zn,Mn)O thin films

Element-specific electronic structure of (Zn,Mn)O thin films with various Mn concentrations has been investigated using X-ray absorption and emission spectroscopy. According to comparison between the experimental spectra and the density functional theory calculations (partial density of states and exchange interactions for various Mn defect configurations), the substitutional Mn impurities do not induce ferromagnetism in (Zn,Mn)O samples. The ferromagnetic properties can be obtained when defect configurations consisting of both substitutional and interstitial Mn atoms are present. The ferromagnetism in ZnO-based magnetic semiconductors is favored to be Ruderman-Kittel-Kasuya-Yoshida type and the established theoretical model is in a good agreement with the X-ray spectroscopic measurements.     

Digital imaging technique for optical emission spectroscopy of a hydrogen arcjet plume

A digital imaging technique has been developed for optical emission spectroscopy measurements of a 1.6-kW hydrogen arcjet plume. Emissions from the Balmer α and β transitions of excited atomic hydrogen were measured with a computer-controlled red-green-blue color CCD detector with and without line-centered bandpass interference filters. A method for extending the effective dynamic range of the detector was developed, whereby images obtained with a wide range of exposure times are combined to form a single composite nonsaturated map of the plume emission structure. The line-of-sight measurements were deconvoluted to obtain the true radial intensity distribution with an inverse Abel transformation. Analysis of the inverted measurements indicates that the upper levels of the Balmer α and β transitions are not thermalized with the electrons in the plasma. The local thermodynamic equilibrium assumption fails for this plasma, and the electron temperature is not equivalent to the apparent excitation temperature obtained when a Boltzmann energy distribution is assumed for the atomic hydrogen excited states.     

Single-photon emission and quantum characterization of zinc oxide defects

Room temperature single-photon emission and quantum characterization is reported for isolated defects in zinc oxide. The defects are observed in thin films of both in-house synthesized and commercial zinc oxide nanoparticles. Emission spectra in the red and infrared, second-order photon correlation functions, lifetime measurements, and photon count rates are presented. Both two- and three-state emitters are identified. Sub-band gap absorption and red emission suggest these defects are the zinc vacancy. These results identify a new source of single photons in a readily available wide band gap semiconductor material which has exceptional electrical, optical, and biocompatibility properties.