Time-gated Spectra Research Articles

Accumulated in-situ spectral information analysis of room-temperature phosphorescence with time-gated bioimaging

This study introduces the time-gated analysis of room-temperature phosphorescence (RTP) for the in-situ analysis of the visible and spectral information of photons. Time-gated analysis is performed using a microscopic system consisting of a spectrometer, which is advantageous for in-situ analysis since it facilitates the real-time measurement of luminescence signal changes. An RTP material hybridized with a DNA aptamer that targets a specific protein enhances the intensity and lifetime of phosphorescence after selective recognition with the target protein. In addition, time-gated analysis allows for the millisecond-scale imaging of phosphorescence signals, excluding autofluorescence, and improves the signal-to-background ratio (SBR) through the accumulation of signals. While collecting the time-gated images and spectra of RTP and autofluorescent materials simultaneously, we develop a method for obtaining phosphorescence signals by means of selective exclusion of autofluorescence signals in simulated or real cell conditions. It is confirmed that the accumulated time-gated analysis can provide ample information about luminescence signals for bioimaging and biosensing applications.

Effect of mixed Frenkel and charge transfer states in time-gated fluorescence spectra of perylene bisimides H-aggregates: Hierarchical equations of motion approach.

We theoretically investigated the effect of mixed Frenkel (F) and charge transfer (CT) states on the spectral properties of perylene bisimide (PBI) derivatives, focusing on the role of strong electron-phonon interactions. The model consists of a four-level system described by the Holstein Hamiltonian coupled to independent local heat-baths on each site, described by Brownian spectral distribution functions. We employ the reduced hierarchical equations of motion (HEOM) approach to calculate the time evolution of the system and compare it to the pure F exciton cases. We compute the absorption and time-gated fluorescence (TGF) spectra for different exciton transfer integrals and F-CT bandgap conditions. The coherence length of excitons (Ncoh) is evaluated employing two different definitions. We observe the presence of an excited hot state peak whose intensity is associated with the delocalization of the excited species and ultrafast dynamics that are solely dependent on the frequency of the local bath. The results indicate that the inclusion of CT states promotes localization of the excitons, which is manifested in a decrease in the intensity of the hot state peak and the 0-1 peak and an increase in the intensity of the 0-0 emission peak in the TGF spectrum, leading to a decrease of Ncoh.

Microsecond-resolved smartphone time-gated luminescence spectroscopy.

Time-gated luminescence spectra are usually measured by laboratory instruments equipped with high-speed excitation sources and spectrometers, which are always bulky and expensive. To reduce the reliance on expensive laboratory instruments, we demonstrate the first, to the best of our knowledge, use of a smartphone for the detection of time-gated luminescence spectra. A mechanical chopper is used as the detection shutter and an optical switch is placed at the edge of the wheel to convert the chopping signal into a transistor-transistor logic (TTL) signal which is used to control the excitation source and achieve synchronization. The time-gated luminescence spectra at different delay times of Eu(TTA)3 powder and the solutions of Eu-tetracycline complex are successfully detected with a temporal resolution of tens of microseconds by the proposed approach. We believe our approach offers a route toward portable instruments for the measurement of luminescence spectra and lifetimes.

Spectrally resolved luminescence lifetime detection for measuring the energy splitting of the long-lived excited states.

Molecular motion plays an important role in the reverse intersystem crossing of thermally activated delayed fluorescence (TADF) materials, since the conformation varies as the molecule vibrates, leading to potential changes in the energies of excited states. Although many theoretical simulations have researched the relationship between the excited states and the molecular conformations, there are still few experimental results showing the energy level difference between different long-lived excited states. Herein, a novel method for measuring spectrally resolved luminescence lifetimes is proposed to detect the energy splitting of the long-lived excited states of a classical TADF molecule, BTZ-DMAC. A set of the time-gated luminescence spectra with different delay times were captured by a spectrograph equipped on an auto-phase-locked system, and then used for lifetime analysis at each wavelength. Unlike traditional measurement techniques, the proposed novel method does not require ultrafast laser, high-speed detector and any phase matching circuitry, thus significantly reducing the cost. This method revealed a definite energy gap between the two excited states of BTZ-DMAC with different lifetimes, indicating different conformations caused by molecular vibration. This low-cost method could be also used to detect many other luminescence materials for investigating the detail mechanisms of multiple excited states.

Auto-phase-locked measurement of time-gated luminescence spectra with a microsecond delay.

Time-resolved techniques are widely used in measuring the spectra and lifetimes of the excited states of molecules. However, the relative apparatus always requires gated detector and phase-matching circuitry, which is expensive to implement and maintain. Herein, a novel auto-phase-locked method for time-gated luminescence (TGL) spectra measurement was developed by adjusting the exciting and detecting optical paths to pass through the same chopper wheel, which simultaneously acted as a pulse generator and detecting shutter. This low-cost system needs no phase-matching circuitry or control system. It can detect TGL spectra with a delay time of only microseconds, demonstrating a high temporal resolution for thermally activated delayed fluorescence detection.

Auto-phase-locked time-gated luminescence detection for background-free upconversion spectra measurement and true-color biological imaging

Time-resolved technique is widely used in biological detection and imaging, since this technique can eliminate the background signals from scattering and short-lived autofluorescence and greatly increase the signal-to-noise ratio. However, the relative apparatus always require pulse source, gated detector and electronic phase matching circuitry, which are expensive to implement and maintain. Herein, a simple method for time-gated upconversion luminescence spectra measurement and biological imaging was developed. By adjusting the exciting and detecting optical paths to pass through the same chopper wheel, only one mechanical chopper was needed, which simultaneously acted as pulse generator and detecting shutter. The phases of each excitation and time gate were synchronized and locked automatically as the optical paths fixed. Therefore, no complex electronic phase matching circuitry or control system was needed. By equipping with a 980 nm CW laser as exciting source, the time-gated spectra of upconversion lanthanide luminescence free from the scattering light was measured. Moreover, smart phones or the human eyes could easily detect the delayed luminescence of these materials, promising the true-color biological imaging with common cameras. This approach could be used in many other time-gated luminescence detection for long-lived luminescence materials and probes excited by other light sources.

Defect specific luminescence dead layers in CdS and CdSe

CdS and CdSe are often used in optoelectronic devices whose effectiveness may be dictated by defects in the near surface region. Luminescence is one of the main tools for studying such defects. The energy dependence of the X-ray excited optical luminescence (XEOL) spectra of these materials enables the extraction of the depth dependence of the defect distribution. Normal and time-gated XEOL spectra were obtained from these materials in the energy range 600–1500 eV. We find that the results can best be understood in terms of a luminescence dead layer whose width depends on the position of the defect level in the band gap.

Optimizing a Time-Resolved Spectrometer for All Time Scales

Time-resolved fluorescence spectroscopy is a spectroscopist's most valuable tool for the investigation of excited state dynamics in molecules, complexes, or semi-conductors. In recent years, the study of luminescence properties has gained in popularity in many scientific fields, including Chemistry, Biology, Physics, as well as in Life, Material or Environmental Sciences. The investigations to be carried out in each of these fields impose different requirements. On one side, monitoring dynamic processes in the excited state necessitates high time resolution that can be achieved by fast pulsed lasers and detectors along with appropriate time-correlated single photon counting (TCSPC) units and small monochromators. On the other hand, high spectral resolution is desirable for fluorophore characterization, requiring detectors with high quantum efficiencies, flash lamps for phosphorescence measurements and large monochromators. Up to now, spectrometers have been usually targeted towards either one of these two specifications. Spectrometers equipped with hybrid detectors, versatile TCSPC cards with optional longer time ranges, and pulsed lasers capable of working in a burst mode can offer an combined solution, covering most of the demands of either high time or spectral resolution. We will demonstrate the performance of such a spectrometer in terms of its time resolution, the ability to measure long decays and record time-gated spectra using laser drivers with burst capabilities. This type of instrument is of great value for analytical facilities in research centers, as it offers a wide range of possible spectroscopic applications in a single, easy to use instrument.

Mid-Atomic-Number Cylindrical Wire Array Precursor Plasma Studies on Zebra

Precursor plasmas from low wire number cylindrical wire arrays (CWAs) were previously shown to radiate at temperatures >300 eV for Ni-60 (94% Cu and 6% Ni) wires in experiments on the 1-MA Zebra generator. Continued research into precursor plasmas has studied additional midatomic-number materials including Cu and Alumel (95% Ni, 2% Al, 2% Mn, and 1% Si) to determine if the >300 eV temperatures are common for midatomic-number materials. In addition, current scaling effects were observed by performing CWA precursor experiments at an increased current of 1.5 MA using a load current multiplier. The results show an increase in a linear radiation yield of ~50% (16 versus 10 kJ/cm) for the experiments at increased current. However, plasma conditions inferred through the modeling of X-ray time-gated spectra are very similar for the precursor plasma in both current conditions.

Extreme ultraviolet spectrometer for the Shenguang III laser facility.

An extreme ultraviolet spectrometer has been developed for high-energy density physics experiments at the Shenguang-III (SG-III) laser facility. Alternative use of two different varied-line-spacing gratings covers a wavelength range of 10-260 Å. A newly developed x-ray framing camera with single wide strip line is designed to record time-gated spectra with ~70 ps temporal resolution and 20 lp/mm spatial resolution. The width of the strip line is up to 20 mm, enhancing the capability of the spatial resolving measurements. All components of the x-ray framing camera are roomed in an aluminum air box. The whole spectrometer is mounted on a diagnostic instrument manipulator at the SG-III laser facility for the first time. A new alignment method for the spectrometer based on the superimposition of two laser focal spots is developed. The approaches of the alignment including offline and online two steps are described. A carbon spectrum and an aluminum spectrum have been successfully recorded by the spectrometer using 2400 l/mm and 1200 l/mm gratings, respectively. The experimental spectral lines show that the spectral resolution of the spectrometer is about 0.2 Å and 1 Å for the 2400 l/mm and 1200 l/mm gratings, respectively. A theoretical calculation was carried out to estimate the maximum resolving power of the spectrometer.

Variable-Temperature Time-Resolved Emission Spectra Studies of Random Pyrene Urethane Methacrylate Copolymers with High Pyrene Incorporation

A series of random co-polyurethane methacrylate comb polymers with pyrene (Py) and 3-pentadecylphenol (PDP) as pendant units were prepared by free radical polymerization. The pyrene labeling was varied from 1 to 100 mol %. The excimer emission of these copolymers were studied as a function of both time and temperature using time-resolved emission spectra (TRES) experiments and variable-temperature steady-state fluorescence measurements. Variable-temperature steady-state as well as decay experiments showed that the contribution from excimers via diffusional encounters increased at the cost of pyrene monomer as the temperature increased until ∼50 °C; beyond which nonradiative losses predominated. TRES collected at 25 and 70 °C were compared to study the nature and origin of emitting species as a function of pyrene loading. TRES at 25 °C clearly indicated the presence of ground-state pyrene dimers with emission centered at ∼435 nm which soon gave way to emission centered around 465 and 485 nm in the time-gated spectra collected at higher time intervals. In TRES collected at 70 °C, excimer emission centered at 465 and 485 nm was very high even at short time scales. The lowest pyrene loaded polymer PIHPDP-1Py did not exhibit excimer emission in the TRES collected at 25 °C as well as 70 °C.

A soft x-ray transmission grating imaging-spectrometer for the National Ignition Facility

A soft x-ray transmission grating spectrometer has been designed for use on high energy-density physics experiments at the National Ignition Facility (NIF); coupled to one of the NIF gated x-ray detectors it records 16 time-gated spectra between 250 and 1000 eV with 100 ps temporal resolution. The trade-off between spectral and spatial resolution leads to an optimized design for measurement of emission around the peak of a 100-300 eV blackbody spectrum. Performance qualification results from the NIF, the Trident Laser Facility and vacuum ultraviolet beamline at the National Synchrotron Light Source, evidence a <100 μm spatial resolution in combination with a source-size limited spectral resolution that is <10 eV at photon energies of 300 eV.

Modeling of K-shell Al and Mg radiation from compact single, double planar and cylindrical alloyed Al wire array plasmas produced on the 1 MA Zebra generator at UNR

Radiative emission from alloyed Al single, double and compact cylindrical wire arrays have been studied using the 1 MA Zebra UNR generator. Single planar wire arrays using ten wires and double planar wire arrays and compact cylindrical wire arrays (CCWA) that both had sixteen wires were utilized. The wire composition is Al-5056 (95% of Al and 5% of Mg). We have observed that implosion of these alloyed Al wire loads generated optically thick Al plasmas that can be diagnosed using K-shell Mg lines. In particular, among the considered loads, the K-shell lines of Al from implosions of the double planar wire arrays have the highest optical depth for He-like Al resonance transitions, which occurred near the stagnation phase. X-ray time-gated and time-integrated spectra and pinhole images as well as photoconductive detectors signals were analyzed to provide information on the plasma parameters; electron temperatures and densities, implosion dynamics features and power and yields of the X-ray radiation. Previously developed non-LTE models were applied to model axially-resolved time-integrated, as well as time-gated spatially-integrated, K-shell spectra from Al and Mg. The derived time-dependent electron temperature, density and axial opacity were studied and compared. In addition, the wire ablation dynamics model (WADM) was used to calculate the kinetic energy of the plasma, which with the aid of a Local Thermal Equilibrium (LTE) magneto-hydrodynamics (MHD) simulation, allowed to estimate the precursor and stagnated z-pinch plasma electron temperatures from implosions of wire array loads.

Study on K-shell X-ray production of double-shellneon gas puff Z-pinch

The main results of investigation on K-shell X-ray production of double-shell neon gas puff Z-pinch, driven by Qiangguang-I facility (1.6 MA, 70 ns), are reported. The exit radii of the outer and inner shells are 1.5—1.4 cm and 0.75—0.6 cm, respectively. Both shells have a throat width of 0.32 mm, while the ratio of the throat radii is 2.8 ∶1, to which the mass ratio would be approximately equal for identical plenum pressures. K-shell yield and peak power up to 7 kJ and 0.28 TW, respectively, for a 20 ns full width at half maximum pulse have been obtained with about 120 ns implosions, the load mass per unit length of which are estimated to be 60—70 μg/cm. Time-resolved X-ray images show that RT instability during the implosion stage has been well suppressed, resulting in a final pinch diameter compressed to less than 2.5 mm. The final implosion velocity exceeds 25 cm/μs. K-shell yields and peak powers are largely reduced with longer implosion time. For shots with lower mass, i.e. 28—63 μg/cm, the electron temperature inferred from time-gated K-shell spectra should be greater than 500 eV, implying an overheated plasma column being formed in the stagnation stage. While for shots with load mass of 72—80 μg/cm, time resolved electron temperatures are in the range of 300—400 eV. The inferred ion densities of the K-shell emitting region are in the range of (3—9)×1019 cm-3, which have been used to calculate the mass fractions that contribute to K-shell radiation. Those shots with near 7 kJ yields also have maximum K-shell emitting load mass (about 46 μg/cm).

Three-Dimensional Light Bullets in Arrays of Waveguides

We report the first experimental observation of three-dimensional light bullets, excited by femtosecond pulses in a system featuring quasi-instantaneous cubic nonlinearity and a periodic, transversally modulated refractive index. Stringent evidence of the excitation of light bullets is based on time-gated images and spectra which perfectly match our numerical simulations. Furthermore, we reveal a novel evolution mechanism forcing the light bullets to follow varying dispersion or diffraction conditions, until they leave their existence range and decay.

Studies of Radiative and Implosion Characteristics From Brass Planar Wire Arrays

Experiments with single-planar wire arrays (SPWA) and double PWAs (DPWAs) with brass 310 wires were carried out on the 1-MA Zebra generator at the University of Nevada, Reno. Brass 310 (70% Cu and 30% Zn) PWAs have either 10 or 16 wires with diameters of 10.9 or 7.62 ?m, respectively. The diagnostic suite included a bolometer, fast X-ray detectors, an axially resolved time-integrated spectrometer, a time-gated spectrometer, a time-gated pinhole camera, and a streak camera. A wire dynamic model was applied to study implosion characteristics, and non-LTE Cu and Zn kinetic models were used to model L-shell radiation from brass. The analysis of the time-gated spectra showed a correlation between the modeled electron temperature and the X-ray signal, and it agrees well with the maximum values from the time-integrated spatially resolved spectra. Modeling of time-gated and time-integrated spectra from brass PWAs indicates stronger opacity effects in L-shell lines for DPWAs.

Study of Electron Beams in Wire Arrays at 1-MA $Z$-Pinch Generators

We analyzed the characteristics of energetic electron beams produced by implosions of multiplanar wire arrays, nested cylindrical wire arrays (NCWAs), and compact cylindrical wire arrays (CCWAs), as well as X-pinches. In this paper, filtered soft and hard X-ray (HXR) diodes, spatially resolved time-integrated and time-gated spatially integrated LiF crystal spectrometers, and a Faraday cup were fielded to study the time evolution and spatial distribution of electron beams. Observed Faraday cup signals (electron cutoff energy, with EB from 42 to 250 keV) always coincide with HXR signals, and their pulse shape is similar to the shape of HXR pulses. The dependence of the total energy of the electron beam (Eb) on the wire material and the geometry of the wire-array load was studied. The electron-beam energies increase with the atomic number of the wire material. Aluminum tracer wires were found to decrease Eb in loads with Cu, Mo, or W wires. The intensity of cold K- and L-shell time-gated spectra correlate with corresponding amplitudes of HXR peaks and Faraday cup signals. The timing of correlation between the onset of energetic electron beams, HXR generation, and appearance of trailing mass for NCWAs and CCWAs is presented and discussed.

Investigation of characteristics of hard x-rays produced during implosions of wire array loads on 1.6 MA Zebra generator

Experimental study of the characteristics of hard x-ray (HXR) emission from multi-planar wire arrays and compact-cylindrical wire arrays (CCWA) plasmas on the 1.6 MA Zebra generator at UNR has been carried out. The characteristics of HXR produced by multi-planar wire arrays such as single, double, and triple planar as well as compact-cylindrical wire arrays made from Al, Cu, brass, Mo, and W were analyzed. Data from spatially resolved time-integrated and spatially integrated time-gated x-ray spectra recorded by LiF spectrometers, x-ray pinhole images, and signals from fast x-ray detectors have been used to study spatial distribution and time history of HXR emission with different loads. The dependence of the HXR yield and power on the wire material, geometry of the load and load mass is observed. Both HXR yield and power are minimum for Al and maximum for W loads. The HXR yield increases with the rise of the atomic number of the material for all loads. The presence of aluminum wires in the load with the main material such as Cu, Mo, or W in combined wire arrays decreases HXR yield. For W plasma, the intensity of cold L-shell spectral lines (1–1.5 Å) correlates with corresponding amplitude of HXR signals which may suggest the evidence of generation of electron beams in plasma. It is found that HXRs are generated from different plasma regions by the interaction of electron-beam with the plasma trailing mass, with the material of anode and due to thermal radiation from plasma bright spots. The theoretical assumption of thermal mechanism of HXR emission predicts the different trends for dependency of HXR power on atomic number and load mass.

Time resolved studies of decay of the XeI 2(IP) complexes

Results of the first studies of temporal behavior of luminescence in the λ = 235–275 nm and λ = 315–350 nm spectral ranges following optical-optical double resonance (OODR) excitation of I 2 + Xe mixtures to the I 2(f, v f = 9, J f ≈ 55) state as well as time-gated luminescence spectra measured with Δ t = 10–70 ns time delay from the beginning of the laser probe pulse, I 2 ( f, v f , J f ← hv p B, v B , J B ) have been described. The spectra look as quasi-continua superimposed with transition bands from the optically and collisionally populated I 2(f, v f = 9, J f ≈ 55) and I 2(F, v F = 1–11) states. The temporal histories of luminescence at the bands and quasi-continua differ significantly. It is shown that, to describe the quasi-continuum in the λ = 315–350 nm time-gated experimental spectra, transitions other than the I 2(f, v f → B, v B) one have to be used. The I 2(f and F) vibrational state distributions observed in experiments can be formed as result of predissociation of long-life XeI 2(IP) complexes. The quasi-continuum in the λ ≈ 330–350 nm spectral ranges can belong to the XeI 2(f → B) transition.

X-ray diagnostics of imploding plasmas from planar wire arrays composed of Cu and few tracer Al wires on the 1MA pulsed power generator at UNR

Tracer aluminum alloyed wires (Al5056) are used to provide additional information for x-ray diagnostics of implosions of Cu planar wire arrays (PWAs). Specifically, the analysis of combined PWA experiments using the extensive set of x-ray diagnostics is presented. In these experiments, which were conducted at the 1MA pulsed power generator at University of Nevada, Reno, the Z-pinch load consisted of several (eight) Cu alloyed (main material) and one to two Al alloyed (tracer) wires mounted in a single plane row or double parallel plane rows, single planar wire array (SPWA) or double planar wire array (DPWA), respectively. The analysis of x-ray spatially resolved spectra from the main material indicates the increase in the electron temperature T(e) near the cathode. In general, the axial gradients in T(e) are more pronounced for SPWA than for DPWA due to the more "columnlike" plasma formation for SPWA compared to "hot-spot-like" plasma formation for DPWA. In addition, x-ray spectra from tracer wires are studied, and estimated plasma parameters are compared with those from the main material. It is observed that the x-ray K-shell Al spectra manifest more opacity features for the case of SPWA with about 18% of Al mass (to the total load mass) compared to the case of DPWA with about 11% of Al mass. The analysis of time-gated spectra shows that the relative intensity of the most intense K-shell Al line, small before the x-ray burst, increases with time and peaks close to the maximum of the sub-keV signal.