Laser detection systems

Most of the time-resolved emission spectroscopy setups are home made in the sense that they are built from individual devices (laser, detection system,. ..) hence they are not of a plug and press type, so that their exact characteristics may vary from one installation to the other. Some of these differences have no impact on the overall capabilities of the system but some have a drastic influence on the way the collected data are processed and analysed. This aspect will be detailed in the next section, while this section deals with a general description of the apparatus. The most basic type of apparatus will be described, with no reference to sophisticated techniques such as Time Correlated Single Photon Counting or Circularly Polarized Luminescence devices. 

Raman Scattaring. Althongh the Raman effect was first reported in 1928 (18,19), its utility as a characterization tool was not realized until the advent of lasers in the early 1960s (20). With the recent advances in lasers, detection systems, and spectrometer design, a tremendons potential exists for use of the Raman technique as a characterization technique. Since it is a scattering techniqne, samples such as powder, film, solid, filament, or solntion can all be studied... 

A new cyanide dye for derivatizing thiols has been reported (65). This thiol label can be used with a visible diode laser and provide a detection limit of 8 X 10 M of the tested thiol. A highly sensitive laser-induced fluorescence detector for analysis of biogenic amines has been developed that employs a He—Cd laser (66). The amines are derivatized by naphthalenedicarboxaldehyde in the presence of cyanide ion to produce a cyanobenz[ isoindole which absorbs radiation at the output of He—Cd laser (441.6 nm). Optimization of the detection system yielded a detection limit of 2 x 10 M. 

For SFM, maintaining a constant separation between the tip and the sample means that the deflection of the cantilever must be measured accurately. The first SFM used an STM tip to tunnel to the back of the cantilever to measure its vertical deflection. However, this technique was sensitive to contaminants on the cantilever." Optical methods proved more reliable. The most common method for monitoring the defection is with an optical-lever or beam-bounce detection system. In this scheme, light from a laser diode is reflected from the back of the cantilever into a position-sensitive photodiode. A given cantilever deflection will then correspond to a specific position of the laser beam on the position-sensitive photodiode. Because the position-sensitive photodiode is very sensitive (about 0.1 A), the vertical resolution of SFM is sub-A. 

The LIMS technique is rarely used for quantitative elemental analysis, since other techniques such as EPMA, AES or SIMS are usually more accurate. The limitations of LIMS in this respect can be ascribed to the lack of a generally valid model to describe ion production from solids under very brief laser irradiation. Dynamic range limitations in the LIMS detection systems are also present, and will be discussed below. 

A modern laser Raman spectrometer consists of four fundamental components a laser source, an optical system for focusing the laser beam on to the sample and for directing the Raman scattered light to the monochromator entrance slit, a double or triple monochromator to disperse the scattered light, and a photoelectric detection system to measure the intensity of the light passing through the monochromator exit slit (Fig. 7). 

A Q-switched Nd YAG laser (7 ns pulse duration, Quanta-Ray DRC-1A) operated at 10 Hz was used as a light source. The 1064 nm fundamental was frequency doubled to 532 nm for some experiments. In all experiments reported here a geometry was used which focused the laser beam in front of the entrance window of the sample cell such that the laser beam was diverging as it passed through the sample cell. In this geometry the laser beam was about 3 mm in diameter at the region viewed by the light detection system. 

Since there are a large number of different experimental laser and detection systems that can be used for time-resolved resonance Raman experiments, we shall only focus our attention here on two common types of methods that are typically used to investigate chemical reactions. We shall first describe typical nanosecond TR spectroscopy instrumentation that can obtain spectra of intermediates from several nanoseconds to millisecond time scales by employing electronic control of the pnmp and probe laser systems to vary the time-delay between the pnmp and probe pnlses. We then describe typical ultrafast TR spectroscopy instrumentation that can be used to examine intermediates from the picosecond to several nanosecond time scales by controlling the optical path length difference between the pump and probe laser pulses. In some reaction systems, it is useful to utilize both types of laser systems to study the chemical reaction and intermediates of interest from the picosecond to the microsecond or millisecond time-scales. 

The basic components include a Nd YAG pulsed laser system which is coaxial with a He Ne pilot laser and visible light optical system. The latter system enables the analytical area of interest to be located. The TOF-MS has a flight path of 2m in length, with an ion detection system that includes an electron multiplier detector, a multichannel transient recorder, together with a computer acquisition and data processing system. 

Fig. 1. Schematic diagram of the multimass ion imaging detection system. (1) Pulsed nozzle (2) skimmers (3) molecular beam (4) photolysis laser beam (5) VUV laser beam, which is perpendicular to the plane of this figure (6) ion extraction plate floated on V0 with pulsed voltage variable from 3000 to 4600 V (7) ion extraction plate with voltage Va (8) outer concentric cylindrical electrode (9) inner concentric cylindrical electrode (10) simulation ion trajectory of m/e = 16 (11) simulation ion trajectory of rri/e = 14 (12) simulation ion trajectory of m/e = 12 (13) 30 (im diameter tungsten wire (14) 8 x 10cm metal mesh with voltage V0] (15) sstack multichannel plates and phosphor screen. In the two-dimensional detector, the V-axis is the mass axis, and V-axis (perpendicular to the plane of this figure) is the velocity axis (16) CCD camera.

Other types of atmospheric pressure ionisation detectors are available including APPI (photon ionisation) and MALDI (matrix-assisted laser desorption ionisation). More conventional detection systems for LC include UV absorption, fluorescence and evaporative light scattering. Developments in column packings,... 

Thus, the region 2100-1830 cm 1 can be covered. This allows us to monitor CO(v,J) by resonance absorption and various M(CO)n [n = 3-6] as a result of near coincidences between the CO laser lines and the carbonyl stretching vibrations of these species. The temporal response of the detection system is ca. 100 ns and is limited by the risetime of the InSb detector. Detection limits are approximately 10 5 torr for CO and M(CO)n. The principal limitation of our instrumentation is associated with the use of a molecular, gas discharge laser as an infrared source. The CO laser is line tuneable laser lines have widths of ca. lO cm 1 and are spaced 3-4 cm 1 apart. Thus, spectra can only be recorded point-by-point, with an effective resolution of ca. 4 cm 1. As a result, band maxima (e.g. in the carbonyl stretching... 

The chiral amines (55) were first derivatized by conventional reaction with fluorescene-isothio-cyanate (57) leading to fluorescein-active compounds (58) (Equation (9)) that enable a sensitive detection system, specifically laser-induced fluorescence detection (LIF), to be used.90 Although... 

In Fig. 3.5A a comparison between time-gated detection and TCSPC is shown. The time-gated detection system was based on four 2 ns wide gates. The first gate opened about 0.5 ns after the peak of the excitation pulse from a pulsed diode laser. The TCSPC trace was recorded using 1024 channels of 34.5 ps width. The specimen consisted of a piece of fluorescent plastic with a lifetime of about 3.8 ns. In order to compare the results, approximately 1700-1800 counts were recorded in both experiments. The lifetimes obtained with TG and TCSPC amounted to 3.85 0.2 ns and 3.80 0.2 ns respectively, see Fig. 3.5B. Both techniques yield comparable lifetime estimations and statistical errors. 

A laser-based detection system for NO2 gas (which is an industrial hazard and common environmental pollutant) was developed by Koybayashi et al.4. This was achieved by splitting light, from an Ar-ion multi-line laser, into two paths, one passing through a measurement gas, and the other being transmitted directly to the measurement unit as a reference signal. The detection unit contained two filters to separate the two chosen laser lines, and these were then detected on separate optical receivers. One of these chosen laser lines coincided with a strong absorption line in the NO2... 

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