Backscattering geometry

Power (mW) Beam Dimensions at Sample Po (W/cm ) Pd (photons/sec cm ) Pd, Relative to 1 mm circle 

As noted earlier, the 180° backscattered geometry is experimentally convenient and has become quite common in commercial instruments. Most fiber-optic probes and Raman microscopes also use 180° backscattered geometry, so similar principles apply in all three sampling categories. 

Pipe with optical sample stream window 

The spectrometer depth of field, 8a, is the same parameter that applies to photography and depends primarily on the // of the collection optics. One expression for 8a is given by Eq. (6.1), where e is the blur diameter (1)  

The laser has a depth of focus that depends on the laser divergence and the focal length of the focusing lens, /i (e.g., LI in Fig. 6.4). The minimum spot 

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Raman microscopy is more developed than its IR counterpart. There are several reasons for this. First, the diffraction limit for focusing a visible beam is about 10 times smaller than an IR beam. Second, Raman spectroscopy can be done in a backscattering geometry, whereas IR is best done in transmission. A microscope is most easily adapted to a backscattermg geometry, but it is possible to do it in transmission. 

Raman spectroscopy is a very convenient technique for the identification of crystalline or molecular phases, for obtaining structural information on noncrystalline solids, for identifying molecular species in aqueous solutions, and for characterizing solid—liquid interfaces. Backscattering geometries, especially with microfocus instruments, allow films, coatings, and surfaces to be easily measured. Ambient atmospheres can be used and no special sample preparation is needed. 

Fig. 3.19 Schematic illustration of the measurement geometry for Mossbauer spectrometers. In transmission geometry, the absorber (sample) is between the nuclear source of 14.4 keV y-rays (normally Co/Rh) and the detector. The peaks are negative features and the absorber should be thin with respect to absorption of the y-rays to minimize nonlinear effects. In emission (backscatter) Mossbauer spectroscopy, the radiation source and detector are on the same side of the sample. The peaks are positive features, corresponding to recoilless emission of 14.4 keV y-rays and conversion X-rays and electrons. For both measurement geometries Mossbauer spectra are counts per channel as a function of the Doppler velocity (normally in units of mm s relative to the mid-point of the spectrum of a-Fe in the case of Fe Mossbauer spectroscopy). MIMOS II operates in backscattering geometry circle), but the internal reference channel works in transmission mode...

Because instrument volume and experiment time must both be minimized for a planetary Mossbauer spectrometer, it is desirable in backscatter geometry to illuminate as much of the sample as possible with source radiation. However, this... 

Fig. 7.73 Mossbauer spectra of Pt (99 keV) in ferromagnetic alloys measured in backscattering geometry with the scatterer kept at 29K. The count rate at infinite velocity is normalized to 1 (from [330])...

Cosine smearing. Because instrument volume and experiment time must both be minimized for a planetary Mossbauer spectrometer, it is desirable in backscatter geometry to illuminate as much of the sample as possible with source radiation. However, this requirement at some point compromises the quality of the Mossbauer spectrum because of an effect known as cosine smearing [327, 348, 349] (see also Sects. 3.1.8 and 3.3). The effect on the Mossbauer spectrum is to increase the linewidth of Mossbauer peaks (which lowers the resolution) and shift their centers outward (affects the values of Mossbauer parameters). Therefore, the diameter of the source y-ray beam incident on the sample, which is determined by a... 

Figure 7.5 Raman spectra of a series of tablets with different coatings to illustrate improvements in spectral quality using transmission-mode instead of conventional backscatter geometry. Bands from the capsule shell are marked with a symbol. Reprinted from Matousek et al. (2007) [8] with permission from John Wiley Sons, Ltd.

Fig. 3.12. Non-invasive Raman spectra of pharmaceutical capsules. The spectra were obtained using a laboratory instrument configured in the transmission Raman geometry and a standard commercial Raman microscope (Renishaw) in conventional backscattering geometry. The Raman spectra of an empty capsule shell (lowest trace) and the capsule content itself (top trace, the capsule content was transferred into an optical cell) are shown for comparison. The dashed lines indicate the principal Raman bands of the capsule and of the API (this figure was published in [65], Copyright Elsevier (2008))...

Using a ring-disk probe (also called inverse SORS) in backscattered geometry we have been able to reach bone about 6 mm below the skin [60]. Mineral/matrix ratios are accurately (<4% relative error) reproduced if a protocol for optimizing the ring/disk spacing is followed [62]. 

Samples were characterized by X-ray diffraction, magnetic susceptibility and chemical analysis with some results summarized in Table 1. The electrical resistivity measurements were made down to 80 K using a four-probe method. Raman scattering experiments used the excitation line A = 514.5 nm of an Ar+ laser in a quasi-backscattering geometry. The laser power of 5 mW was focused to a 0.1 mm diameter spot on the (010) surface. The averaged laser power density amounts to 6 105 W/m2 which is much less compared to earlier Raman studies in manganites [12-15],... 

The experimental setup for matrix Raman spectroscopy is essentially the same as that for matrix IR spectroscopy. The major difference lies in optical geometry. Namely, backscattering geometry must be employed in Raman spectroscopy since the matrix gas and sample vapor are deposted on a cold metal (Cu, Al) surface. Figure 3-27 shows the optical arrangement... 

The Raman spectra were recorded in the backscattering geometry on a Labram I (Jobin-Yvon, Horiba Group, France) microspectrometer in conjunction with a confocal microscope. To avoid any thermal photochemical effect, we have used a minimum intensity laser power on sample of 370 pW with the 514.5 nm incident line from an Ar-Kr laser from Spectra Physics. Detection was achieved with an air cooled CCD detector and a 1800 grooves/mm, giving a spectral resolution of 4 cm-1. An acquisition time of 120 s was used for each spectrum. The confocal aperture was adjusted to 200 pm and a 50 X objective of 0.75 numerical aperture was used. 

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