Luminescence decay times

K. H. Drexhage. Influence of a dielectric interface on fluorescence decay time / Luminesc, 1970, 1/2,693-701. 

Luminescent Pigments. Luminescence is the abihty of matter to emit light after it absorbs energy (see Luminescent materials). Materials that have luminescent properties are known as phosphors, or luminescent pigments. If the light emission ceases shortly after the excitation source is removed (<10 s), the process is fluorescence. The process with longer decay times is referred to as phosphorescence. 

The triplet-state energy level of oxytetracycline, the excitation maximum (412 nm), lifetimes of Eu-OxTc (58 p.s) and Eu-OxTc-Cit (158 p.s), were determined. A 25-fold luminescence enhancement at 615 nm occurs upon addition of citrate within a short 5-min incubation time at neutral pH. It s accompanied by a threefold increase of the luminescence decay time. The optimal conditions for determination of OxTc are equal concentrations of Eu(III) and citrate (C = T lO mol-E ), pH 7.2. Eor determination of citrate, the optimal conditions concentrations of Eu(HI) and OxTc are 1 0,5 (Cg = MO Huol-E-i, = 5-10-HuohE-i) at pH 7.2. 

Requirements for standards used In macro- and microspectrofluorometry differ, depending on whether they are used for Instrument calibration, standardization, or assessment of method accuracy. Specific examples are given of standards for quantum yield, number of quanta, and decay time, and for calibration of Instrument parameters. Including wavelength, spectral responslvlty (determining correction factors for luminescence spectra), stability, and linearity. Differences In requirements for macro- and micro-standards are considered, and specific materials used for each are compared. Pure compounds and matrix-matched standards are listed for standardization and assessment of method accuracy, and existing Standard Reference Materials are discussed. 

Definition and Uses of Standards. In the context of this paper, the term "standard" denotes a well-characterized material for which a physical parameter or concentration of chemical constituent has been determined with a known precision and accuracy. These standards can be used to check or determine (a) instrumental parameters such as wavelength accuracy, detection-system spectral responsivity, and stability (b) the instrument response to specific fluorescent species and (c) the accuracy of measurements made by specific Instruments or measurement procedures (assess whether the analytical measurement process is in statistical control and whether it exhibits bias). Once the luminescence instrumentation has been calibrated, it can be used to measure the luminescence characteristics of chemical systems, including corrected excitation and emission spectra, quantum yields, decay times, emission anisotropies, energy transfer, and, with appropriate standards, the concentrations of chemical constituents in complex S2unples. 

Nishimura, H., Yamaoka, T., Hattori, K., Matsui, A. and Mizuno, K. (1985) Wavelength-dependent decay times and time-dependent spectra of the singlet-exciton luminescence in anthracene crystals./. Phys. Soc. Jpn., 54, 4370-4381. Matsui, A. and Nishimura, H. (1980) Luminescence of free and self trapped excitons in pyrene. J. Phys. Soc. Jpn., 49, 657-663. 

As a matter of fact low-lying MMCT states can also influence radiative transition probabilities. The long decay time of the VO4 luminescence is considerably shortened by the presence of Bi " [27] due to a Bi(IV)-V(IV) MMCT state (see also above). Such effects are very well-known for LMCT states in case of transition-metal ions and lanthanide ions [6]. They will not be discussed here any further. 

According to Ludwig (1968), there is a some similarity between UV- and high-energy-induced luminescence in liquids. In many cases (e.g., p-ter-phenyl in benzene), the luminescence decay times are similar and the quenching kinetics is also about the same. However, when a mM solution of p-terphenyl in cyclohexane was irradiated with a 1-ns pulse of 30-KeV X-rays, a long tail in the luminescence decay curve was obtained this tail is absent in the UV case. This has been explained in terms of excited states produced by ion neutralization, which make a certain contribution in the radiolysis case but not in the UV case (cf. Sect. 4.3). Note that the decay times obtained from the initial part of the decay are the same in the UV- and radiation-induced cases. Table 4.3 presents a brief list of luminescence lifetimes and quantum yields. 

Figure 6. Tip of the 20-pm tip of a fiber optic oxygen microsensor. The tip is coated with a ormosil-type of sol-gel doped with a ruthenium indicator for oxygen that display red luminescence. The sensor measures its decay time as a function of oxygen partial pressure.

Kosch U., Klimant I., Werner T., Wolfbeis O.S., Strategies To Design pH Optodes With Luminescence Decay Times In The Microsecond Time Regime, Anal. Chem. 1998 70 3892-3897. 

The optode transduces the non-optical signal from the environment to the optical one, readable by the photodetector. Various indirect optical sensors and theirs applications are described in literature35. The optode can work as a chemical sensor that detects certain analytes in aqueous solutions or in air on chemical way. It means that changes in the environment cause the changes in the photosensitive material, which is immobilized in the optode matrix. These chemical changes influence the observed light intensity (for example, due to absorption) or one can analyze the intensity or time decay of luminescence. There are numbers of publications devoted to the family of optical chemical sensors36. 

Griseofulvin exhibits both fluorescence and luminescence. A report by Neely et al., (7) gives corrected fluorescence excitation (max. 295 nm) and emission (max. 420 nm) spectra, values for quantum efficiency of fluorescence (0.108) calculated fluorescence lifetime (0.663 nsec) and phosphorescence decay time (0.11 sec.). The fluorescence excitation and emission spectra are given in Figure 7. 

Lifetime [3,9-11] based sensors rely on the determination of decay time of the fluorescence or phosphorescence. Typically, the fluorescence lifetime is 2-20 ps and phosphorescence lifetime is 1 ps to 10 s. Lifetime-based sensors utilize the fact that analytes influence the lifetime of the fluorophore. Thus all dynamic quenchers of luminescence or suitable quenchers can be assayed this way. The relationship between lifetimes in the absence (t0) and presence (t) of a quencher is given by Stern and Volmer ... 

Wolfbeis OS, Klimant I, Werner T, Huber C, Kosch U, Krause C, Neurauter G, Diirkop A (1998) Set of luminescence decay time based chemical sensors for clinical applications. Sens Actuators B 51 17-24... 

Have good photostability. Photostability is particularly critical if high light intensities are used for interrogation (such as in microscopy or fiber-optic microsensors) or if the measurements are performed over a long time. Photodegradation always affects luminescence intensity but is usually less critical in case of the decay time measurements since this parameter can remain unaffected by photobleaching. 

Measurement of luminescence decay time represents another method of self-referencing. The method is widely used for the indicators that possess luminescence decay times in the microsecond and millisecond domain which can be interrogated... 

Mayr T, Moser C, Klimant I (2007) Luminescence decay time encoding of magnetic micro spheres for multiplexed analysis. Anal Chim Acta 597 137-144... 

Anodization of Si in HF under an applied magnetic field produces an enhancement of the PL efficiency at RT, accompanied by an enhanced porosity compared to PS samples prepared without an applied field. The degree of polarization of the emitted PL is reduced for field-assisted preparation [Na3]. At low temperatures (4.2 K), the Stokes shift and the decay time of the PL are found to be increased, if compared to PS formed under zero magnetic field. This has been interpreted as Zeeman splitting of the spin-triplet exciton states. It indicates that the ground state of the luminescing silicon crystallite is a triplet state [Kol3]. 

The surface-state model, in which the luminescent recombination occurs via surface states, was proposed to explain certain properties of the PL from PS, for example long decay times or sensitivity of the PL on chemical environment. In the frame of this model the long decay times are a consequence of trapping of free carriers in localized states a few hundred meV below the bandgap of the confined crystallite. The sensitivity of the PL to the chemical environment is interpreted as formation of a trap or change of a trap level by a molecule bonding to the surface of a PS crystallite. The surface-state model suffers from the fact that most known traps, e.g. the Pb center, quench the PL [Me9], while the kinds of surface state proposed to cause the PL could not be identified. 

The previous formula indicates that the radiative lifetime tq (and hence the radiative rate A) can be determined from luminescence decay-time measurements if the quantum efficiency rj is measured by an independent experiment. Methods devoted to the measurement of quantum efficiencies are given in Section 5.7. 

At this point it is important to mention that the experimental setup used for luminescence decay-time measurements is similar to that of Figure 1.8, although the light source must be pulsed (alternatively, a pulsed laser can be used) and the detector must be connected to a time-sensitive system, such as an oscilloscope, a multichannel analyzer, or a boxcar integrator (see Chapter 2). 

Figure 1.12 The schematic temporal decay of luminescence, showing a gate of width At at a delay time t.

Most optical centers show luminescence decay times in the nanoseconds-milliseconds range. However, many other physical processes involved in optical spectroscopy are produced in the picoseconds-femtoseconds range, and mnch more complicated instrumentation becomes necessary. For instance, interband Inminescence in solids, which is of particular interest in semiconductors, can involve decay times in the range of picoseconds. Pulses generated from solid state lasers have already reached this femtosecond domain. 

As the concentration quenching results from energy transfer processes, the decay time of the emitting ions is reduced when one concentration quenching mechanism occurs. In general, this decay-time reduction is much easier to measure than the reduction in the quantum efficiency. In fact, the easiest way to detect luminescence concentration quenching is to analyze the lifetime of the excited centers as a function of the concentration. The critical concentration is that for which the lifetime starts to be reduced. 

Observations of the decay time of luminescence from activator atoms in crystals excited by laser pulses have enabled lifetimes of... 

If the 4f5d levels are situated at still lower energy, no 5d->-4f emission is observable. In stead emission from the Pq level occurs. Weber 48) has studied in Y3Al50i2-Pr3+ the nonradiative decay from the luminescent 4f5d level of Pr3+ to the Po,i,2 and i/e level. For temperatures below 250 K the decay time of the 5d - 4/ luminescence is constant and amounts to about 2.10 sec (as is to... 

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