Excitation enhancement factor coupling

Further enhancement can be observed if the exciting light additionally couples into an electronic transition of the adsorbate (surface-enhanced resonance Raman scattering, SERRS). In this case, enhancement factors of... 

Based on our research laboratory s observations of MEF from metals other than silver, MEC from chromium, coppo, nickel and zinc was also studied. Figure 1. 12 shows the enhancement factors for green chemiluminescence from diese metals with various thicknesses. A typical enhancement factor of 2-3-fold is observed from all metal surfaces, vdiich implies that chemically excited states can couple to these plasmon resonant metal particles. It is interesting to note that the chemiluminescence emission is dependent on the amount of reactants in the solution and diminishes once one of the reactants is used up. To test viiether the remainder of the inactive chemiluminescent dye can be excited with an external light source and still emit luminescence, additional experiments were undertaken where the chemiluminescence solution was excited with a laso at 473 nm. Interestingly, the inactive chemiluminescence dye can be optically excited and still emit luminescence with enhancement factors similar to the chemically excited conditions being observed. A detailed investigation of MEC from different metals is currently underway and will be reported in due course. 

Formally, one can think of the Raman transition probability being proportional to the elements of the polarizability tensor of a bound electron as the exciting frequency approaches the resonance frequency, these elements are enhanced in a Lorentz model of the bound electron. A common example of this mechanism is furnished by the ring-breathing (in-plane expansion) modes of porphyrins. Another mechanism, called vibronic enhancement, involves vibrations which couple two electronic excited states. In both mechanisms, the enhancement factors are nearly proportional to the intensities in the absorption spectrum of the adsorbate. 

In summary, it can be said, that fluorophores feel more exciting light compared to standard glass slides and emit more photons per unit time. While signal amplification will reach up to 8 on smooth films enhancement factors up to 200 times have been observed for cluster structures (Figure 26). The reason for this is the fact, that more energy can be coupled into cluster structures due to the additional presence of Mie plasmons, into which most of the energy is coupled. 

An additional effect to consider for SERRS is that of the fluorescence which can occur simultaneously with a RRS process. This is the so-called delayed fluorescence, " which is a radiative decay process for molecules which have relaxed from their initial excited vibrational state of the excited electronic state to the lowest vibrational level of the excited state. Delayed fluorescence can be additionally damped on a rough Ag surface for the same reasons that the RRS process is additionally damped, i.e., by coupling to the surface plasmon resonances. On the other hand, the electromagnetic enhancement factors L (o)L (Oip), will also cause an enhancement of the fluorescence in a similar manner to the Raman process. However, the decay of excited molecules by the surface channel will tend to mitigate the EM fluorescence enhancement effect. Two cases have been discussed in the literature " (a) the case of a molecule with a fluorescence quantum efficiency near unity in the free state, i.e., QE 1, and (b) the case with QE 1. If QE is low (<0.01), the fluorescent emission is estimated to be enhanced by ca. 10 whereas, for QE 1, a surface quenching of fluorescent emission by ca. 10" has been... 

The intrinsic drawback of LIBS is a short duration (less than a few hundreds microseconds) and strongly non-stationary conditions of a laser plume. Much higher sensitivity has been realized by transport of the ablated material into secondary atomic reservoirs such as a microwave-induced plasma (MIP) or an inductively coupled plasma (ICP). Owing to the much longer residence time of ablated atoms and ions in a stationary MIP (typically several ms compared with at most a hundred microseconds in a laser plume) and because of additional excitation of the radiating upper levels in the low pressure plasma, the line intensities of atoms and ions are greatly enhanced. Because of these factors the DLs of LA-MIP have been improved by one to two orders of magnitude compared with LIBS. 

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