Laser ablation materials

Figure 9.2 Schematic diagram of a quadrupole ICP-MS capable of working in either the solution or laser ablation mode. In the solid mode, a vertical laser ablates material from the sample which is mounted on a moveable horizontal stage. In solution mode, the liquid is sucked up into the injection chamber.

On line additions of aqueous standard solutions for the calibration of LA-ICP-MS including a comparison of wet and dry plasma conditions are discussed by O Connor et al.ls For solution calibration of standard solutions the authors used a 100 (xl PFA nebulizer together with a cyclonic spray chamber or a MCN-6000 sample introduction system with desolvator, to study the wet and dry plasma, respectively. A polypropylene Y piece was applied to mix the laser ablated material and the nebulized standard solutions. The authors found that the on line addition of water is the preferred mode of operation for quantification by LA-ICP-MS, i.e., wet plasma is more stable (improved standard deviation of sensitivity ratios). 

Lasers can be used in either pulsed or continuous mode to desorb material from a sample, which can then be examined as such or mixed or dissolved in a matrix. The desorbed (ablated) material contains few or sometimes even no ions, and a second ionization step is frequently needed to improve the yield of ions. The most common methods of providing the second ionization use MALDI to give protonated molecular ions or a plasma torch to give atomic ions for isotope ratio measurement. By adjusting the laser s focus and power, laser desorption can be used for either depth or surface profiling. 

Fundamentally, introduction of a gaseous sample is the easiest option for ICP/MS because all of the sample can be passed efficiently along the inlet tube and into the center of the flame. Unfortunately, gases are mainly confined to low-molecular-mass compounds, and many of the samples that need to be examined cannot be vaporized easily. Nevertheless, there are some key analyses that are carried out in this fashion the major one i.s the generation of volatile hydrides. Other methods for volatiles are discussed below. An important method of analysis uses lasers to vaporize nonvolatile samples such as bone or ceramics. With a laser, ablated (vaporized) sample material is swept into the plasma flame before it can condense out again. Similarly, electrically heated filaments or ovens are also used to volatilize solids, the vapor of which is then swept by argon makeup gas into the plasma torch. However, for convenience, the methods of introducing solid samples are discussed fully in Part C (Chapter 17). 

Some solid materials are very intractable to analysis by standard methods and cannot be easily vaporized or dissolved in common solvents. Glass, bone, dried paint, and archaeological samples are common examples. These materials would now be examined by laser ablation, a technique that produces an aerosol of particulate matter. The laser can be used in its defocused mode for surface profiling or in its focused mode for depth profiling. Interestingly, lasers can be used to vaporize even thermally labile materials through use of the matrix-assisted laser desorption ionization (MALDI) method variant. 

Alternative Thin-Film Fabrication Approaches. Thin films of electronic ceramic materials have also been prepared by sputtering, electron beam evaporation, laser ablation, chemical beam deposition, and chemical vapor deposition (CVD). In the sputtering process, targets may be metal... 

Laser based mass spectrometric methods, such as laser ionization (LIMS) and laser ablation in combination with inductively coupled plasma mass spectrometry (LA-ICP-MS) are powerful analytical techniques for survey analysis of solid substances. To realize the analytical performances methods for the direct trace analysis of synthetic and natural crystals modification of a traditional analytical technique was necessary and suitable standard reference materials (SRM) were required. Recent developments allowed extending the range of analytical applications of LIMS and LA-ICP-MS will be presented and discussed. For example ... 

A somewhat related technique is that of laser ionization mass spectrometry (LIMS), also known as LIMA and LAMMA, where a single pulsed laser beam ablates material and simultaneously causes some ionization, analogous to samples beyond the outer surface and therefore is more of a bulk analysis technique it also has severe quantiBaction problems, often even more extreme than for SIMS. 

In Table 4.3, the Cetac product LSX-200 is the specialized system for coupling with the ICP customer s system. It includes the laser, optical viewing system for exact positioning of the laser focus on a sample surface, and the sample cell mounted on the computer controlled XYZ translation stage. The system is also provided with the appropriate gas tuhing for transport of the ablated material into an ICP-OES/MS. 

Different analytical techniques are used for detection of the elemental composition of the solid samples. The simplest is direct detection of emission from the plasma of the ablated material formed above a sample surface. This technique is generally referred to as LIBS or LIPS (laser induced breakdown/plasma spectroscopy). Strong continuous background radiation from the hot plasma plume does not enable detection of atomic and ionic lines of specific elements during the first few hundred nanoseconds of plasma evolution. One can achieve a reasonable signal-to-noise ra-... 

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. 

The last problem of this series concerns femtosecond laser ablation from gold nanoparticles [87]. In this process, solid material transforms into a volatile phase initiated by rapid deposition of energy. This ablation is nonthermal in nature. Material ejection is induced by the enhancement of the electric field close to the curved nanoparticle surface. This ablation is achievable for laser excitation powers far below the onset of general catastrophic material deterioration, such as plasma formation or laser-induced explosive boiling. Anisotropy in the ablation pattern was observed. It coincides with a reduction of the surface barrier from water vaporization and particle melting. This effect limits any high-power manipulation of nanostructured surfaces such as surface-enhanced Raman measurements or plasmonics with femtosecond pulses. 

D microfabricated reactor devices are typically made by fabrication techniques other than stemming from microelectronics, e.g. by modern precision engineering techniques, laser ablation, wet-chemical steel etching or pEDM techniques. Besides having this origin only, these devices may also be of hybrid nature, containing parts made by the above-mentioned techniques and by microelectronic methods. Typical materials are metals, stainless steel, ceramics and polymers or, in the hybrid case, combinations of these materials. 

Further modification of the above nanostructures is useful for obtaining new functional materials. Thirdly, we apply the dopant-induced laser ablation technique to site-selectively doped thin diblock copolymer films with spheres (sea-island), cylinders (hole-network), and wormlike structures on the nanoscale [19, 20]. When the dye-doped component parts are ablated away by laser light, the films are modified selectively. Concerning the laser ablation of diblock copolymer films, Lengl et al. carried out the excimer laser ablation of diblock copolymer monolayer films, forming spherical micelles loaded with an Au salt to obtain metallic Au nanodots [21]. They used the laser ablation to remove the polymer matrix. In our experiment, however, the laser ablation is used to remove one component of block copolymers. Thereby, we can expect to obtain new functional materials with novel nanostmctures. 

As aforementioned, diblock copolymer films have a wide variety of nanosized microphase separation structures such as spheres, cylinders, and lamellae. As described in the above subsection, photofunctional chromophores were able to be doped site-selectively into the nanoscale microdomain structures of the diblock copolymer films, resulting in nanoscale surface morphological change of the doped films. The further modification of the nanostructures is useful for obtaining new functional materials. Hence, in order to create further surface morphological change of the nanoscale microdomain structures, dopant-induced laser ablation is applied to the site-selectively doped diblock polymer films. 

Hiroshi Fukumura received his M.Sc and Ph.D. degrees from Tohoku University, Japan. He studied biocompatibility of polymers in the Government Industrial Research Institute of Osaka from 1983 to 1988. He became an assistant professor at Kyoto Institute of Technology in 1988, and then moved to the Department of Applied Physics, Osaka University in 1991, where he worked on the mechanism of laser ablation and laser molecular implantation. Since 1998, he is a professor in the Department of Chemistry at Tohoku University. He received the Award of the Japanese Photochemistry Association in 2000, and the Award for Creative Work from The Chemical Society Japan in 2005. His main research interest is the physical chemistry of organic molecules including polymeric materials studied with various kinds of time-resolved techniques and scanning probe microscopes. 

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