Ion impurities

A laser pulse strikes the surface of a specimen (a), removing material from the first layer, A. The mass spectrometer records the formation of A+ ions (b). As the laser pulses ablate more material, eventually layer B is reached, at which stage A ions begin to decrease in abundance and ions appear instead. The process is repeated when the B/C boundary is reached so that B+ ions disappear from the spectrum and C+ ions appear instead. This method is useful for depth profiling through a specimen, very little of which is needed. In (c), less power is used and the laser beam is directed at different spots across a specimen. Where there is no surface contamination, only B ions appear, but, where there is surface impurity, ions A from the impurity also appear in the spectrum (d). 

Plasmas at fusion temperatures cannot be kept in ordinary containers because the energetic ions and electrons would rapidly coUide with the walls and dissipate theit energy. A significant loss mechanism results from enhanced radiation by the electrons in the presence of impurity ions sputtered off the container walls by the plasma. Therefore, some method must be found to contain the plasma at elevated temperature without using material containers. 

Solid-State Lasers. Sohd-state lasers (37) use glassy or crystalline host materials containing some active species. The term soHd-state as used in connection with lasers does not imply semiconductors rather it appHes to soHd materials containing impurity ions. The impurity ions are typically ions of the transition metals, such as chromium, or ions of the rare-earth series, such as neodymium (see Lanthanides). Most often, the soHd material is in the form of a cylindrical rod with the ends poHshed flat and parallel, but a variety of other forms have been used, including slabs and cylindrical rods with the ends cut at Brewster s angle. 

Phosphors usually contain activator ions in addition to the host material. These ions are dehberately added in the proper proportion during the synthesis. The activators and their surrounding ions form the active optical centers. Table 1 Hsts some commonly used activator ions. Some soflds, made up of complexes such as calcium tungstate [7790-75-2] CaWO, are self-activated. Also in many photolurninescence phosphors, the primary activator does not efficiently absorb the exciting radiation and a second impurity ion is introduced known as the sensitizer. The sensitizer, which is an activator ion itself, absorbs the exciting radiation and transfers this energy to the primary activator. 

In order to make an efficient Y202 Eu ", it is necessary to start with weU-purifted yttrium and europium oxides or a weU-purifted coprecipitated oxide. Very small amounts of impurity ions, particularly other rare-earth ions, decrease the efficiency of this phosphor. Ce " is one of the most troublesome ions because it competes for the uv absorption and should be present at no more than about one part per million. Once purified, if not already coprecipitated, the oxides are dissolved in hydrochloric or nitric acid and then precipitated with oxaflc acid. This precipitate is then calcined, and fired at around 800°C to decompose the oxalate and form the oxide. EinaHy the oxide is fired usually in air at temperatures of 1500—1550°C in order to produce a good crystal stmcture and an efficient phosphor. This phosphor does not need to be further processed but may be milled for particle size control and/or screened to remove agglomerates which later show up as dark specks in the coating. 

M. N. Myers, Mbsorption Spectra of Plutonium and Impurity Ions in Nitric Mcid Solution, HW-44744, General Electric Co., 1956. 

In addition to the thermal vacancies, impurity-related vacancies will develop in ionic crystals. When impurity ions have a charge different from ions of like charge which are the crystal s main constituents, part of the lattice sites must remain vacant in order to preserve electroneutrality. Such impurity-type defects depend little on temperature, and their major effects are apparent at low temperatures when few thermal vacancies exist. 

Ion exchange (IX) is a very useful technique for the concentration, the purification and the separation of chemically similar metallic elements present in an aqueous solution. In its most popular form of application, the metal-bearing aqueous solution is passed through a bed of solid organic resin in a particulate form wherein the sorption of the metal ions on the resin takes place by ion-exchange reactions. The pregnant resin is washed free of the entrapped feed solution and then brought into contact with an eluant of suitable composition and volume so that the resin releases the metal ions back to the eluant. The ratio of the volume of the feed and that of the eluant determines the extent of concentration that can be achieved. Purification and separation are achievable if the resin is selective or specific with respect to the metal ions of interest in comparison to impurity ions. 

There is, however, one point where the different experiments do not agree Gougousi et al. found that the plasma decayed faster when the H2 concentration was increased. They concluded this from a large set of data over a significant range of H2 densities and they found the same to be true when Dj ions were studied in the presence of D2. Smith and Spanel carried out tests over a smaller range of H2 concentrations. Their data show the opposite dependence on H2 concentration, but unfortunately the authors discontinued this set of measurements since they became concerned about an increase in the concentration of impurity ions. 

Figure 3. Dependence of analyte ion intensity on concentration. (A) Dependence of total current / on concentration M = mol/L of analyte ion, (Morphine)H+, i.e., MorH+, in solution. (B) Dependence of mass-analyzed MorH+ ion current in counts/s on MorH+ concentration. At low MorH+ concentrations, [MorH+] < 1CT6 M, the dominant electrolyte in the solution are impurity ions Na+ and NH4. In this region MorH+ intensity is proportional to [MorH+] in solution. Mass-analyzed ion intensity was corrected for mass-dependent transmission Tm, of quadrupole. Concentration of morphine hydrochloride given in mol/L (M). From Kebarle, P. Tang, L. Anal. Chem. 1993, 65, 973A, with permission.

The shape of the mass-analyzed gas phase /tot curve is seen to be very similar to that of the capillary current I (Figure 3). An approximate proportionality between the two currents when the concentration is increased is generally observed in this concentration range.45,51 For an analyte concentration above 10 5 M, the intensity of the impurity ions B+ is observed to decrease. This decrease is a consequence of the weak dependence of the capillary current I on the total electrolyte concentration. 

One type of point defect that cannot be entirely eliminated from a solid compound is the substituted ion or impurity defect. For example, suppose a large crystal contains 1 mole of NaCl that is 99.99 mole percent pure and that the 0.01% impurity is KBr. As a fraction, there is 0.0001 mole of both K+ and Br ions, which is 6.02 X 1019 ions of each type present in the 1 mole of NaCl Although the level of purity of the NaCl is high, there is an enormous number of impurity ions that occupy sites in the lattice. Even if the NaCl were 99.9999 mole percent pure, there would still be 6.02 X 1017 impurity cations and anions in a mole of crystal. In other words, there is a defect, known as a substituted ion or impurity defect, at each point in the crystal where some ion other than Na+ or Cl- resides. Because K+ is larger than Na+ and Br is larger than Cl-, the lattice will experience some strain and distortion at the sites where the larger cations and anions reside. These strain points are frequently reactive sites in a crystal. 

A straightforward method is to incorporate ahovalent impurity ions into the crystal. These impurities can, in principle, be compensated structurally, by the incorporation of interstitials or vacancies, or by electronic defects, holes, or electrons. The possibility of electronic compensation can be excluded by working with insulating solids that contain ions with a fixed valence. 

Acceptor dopants are impurity ions of a lower valence than that of the parent ions, as when small amounts of A1203 are incorporated into Ti02, so that the Al3+ ion substitutes for Ti4+. The acceptor species has an effective negative charge, Al i in this example, and the introduction of acceptor species tends to introduce counterbalancing... 

Our approach has been to study a very simple clay-water system in which the majority of the water present is adsorbed on the clay surfaces. By appropriate chemical treatment, the clay mineral kao-linite will expand and incorporate water molecules between the layers, yielding an effective surface area of approximately 1000 m2 g . Synthetic kaolinite hydrates have several advantages compared to the expanding clays, the smectites and vermiculites they have very few impurity ions in their structure, few, if any, interlayer cations, the structure of the surfaces is reasonably well known, and the majority of the water present is directly adsorbed on the kaolinite surfaces. 

For uptake proceeding by isomorphous substitution, the partition coefficient D depends on thermodynamic parameters such as ionic radius of the impurity ions and the phases of the calcium sulfate as well as on kinetics. 

Emerald, Cr " doped beryl, has a beryl structure with the Cr " impurity ions in highly distorted octahedron sites. The discovery of lasing action in emerald stimulated investigation of its luminescence properties. It was established that its tuning range is approximately 730-810 nm, while luminescence consists of a narrow line at 684 nm and a band peaking at 715 nm with similar decay times of 62 ps. The relative intensities of those line and band are different in a- and 7T-polarized spectra (Fabeni et al. 1991). 

Very broadly speaking, two situations have to be considered in explaining devices such as those we have mentioned. In the first, which is relevant to the ruby laser and to phosphors for fluorescent lights, the light is emitted by an impurity ion in a host lattice. We are concerned here with what is essentially an atomic spectrum modified by the lattice. In the second case, which applies to LEDs and the gallium arsenide laser, the optical properties of the delocalised electrons in the bulk solid are important. 

FIGURE 8.5 Sketch of a ruby laser. TABLE 8.1 Impurity ions used in lasers... 

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