Impurity defect

Another type of point defect is the incorporation of an impurity atom. Impurity atoms may replace host atoms in the regular crystal structure, in which case they are called substitutional defects, or they may occupy an interstitial site as interstitial impurities. Impurities are often purposely introduced in a lattice to strengthen it (solid solution hardening) or to otherwise alter its properties, e.g., doping a semiconductor to tailor the number and sign of charge carriers. However, as seen later, it is virtually impossible to completely eliminate unwanted impurity atoms. 

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The second class of atomic manipulations, the perpendicular processes, involves transfer of an adsorbate atom or molecule from the STM tip to the surface or vice versa. The tip is moved toward the surface until the adsorption potential wells on the tip and the surface coalesce, with the result that the adsorbate, which was previously bound either to the tip or the surface, may now be considered to be bound to both. For successful transfer, one of the adsorbate bonds (either with the tip or with the surface, depending on the desired direction of transfer) must be broken. The fate of the adsorbate depends on the nature of its interaction with the tip and the surface, and the materials of the tip and surface. Directional adatom transfer is possible with the apphcation of suitable junction biases. Also, thermally-activated field evaporation of positive or negative ions over the Schottky barrier formed by lowering the potential energy outside a conductor (either the surface or the tip) by the apphcation of an electric field is possible. FIectromigration, the migration of minority elements (ie, impurities, defects) through the bulk soHd under the influence of current flow, is another process by which an atom may be moved between the surface and the tip of an STM. 

Parasitic ferromagnetism is a weak ferromagnetism that accompanies antiferromagnetism, eg, in a-ferric oxide [1309-37-1], a-Fe202. Possible causes include the presence of a smaU amount of ferromagnetic impurities, defects in the crystal, and slight deviations in the directions of the plus and minus spins from the original common axis. 

As mentioned earlier, CL is a powerful tool for the characterization of optical properties of wide band-gap materials, such as diamond, for which optical excitation sources are not readily available. In addition, electron-beam excitation of solids may produce much greater carrier generation rates than typical optical excitation. In such cases, CL microscopy and spectroscopy are valuable methods in identifying various impurities, defects, and their complexes, and in providing a powerful means for the analysis of their distribution, with spatial resolution on the order of 1 pm and less. ... 

The two extremes of ordering in solids are perfect crystals with complete regularity and amorphous solids that have little symmetry. Most solid materials are crystalline but contain defects. Crystalline defects can profoundly alter the properties of a solid material, often in ways that have usefial applications. Doped semiconductors, described in Section 10-, are solids into which impurity defects are introduced deliberately in order to modify electrical conductivity. Gemstones are crystals containing impurities that give them their color. Sapphires and rubies are imperfect crystals of colorless AI2 O3, red. 

The presence of a solvent, especially water, and/or other additives or impurities, often in nonstoichiometric proportions, may modify the physical properties of a solid, often through impurity defects, through changes in crystal habit (shape) or by lowering the glass transition temperature of an amorphous solid. The effects of water on the solid-state stability of proteins and peptides and the removal of water by lyophilization to produce materials of certain crystallinity are of great practical importance although still imperfectly understood. 

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. 

Conduction in these ID metals is vulnerable to impurities, defects and thermal vibrations within each stack. Inter-stack interactions allow for increased dimensionality, and in some cases, superconductivity, by suppressing... 

When in solid solution in the solid state, an impurity will alter the crystallinity by introducing impurity defects into the crystal lattice, thereby changing the thermodynamic and other physical properties of the solid, including the solubility and dissolution rate [2,37]. Prolonged equilibration of the solid state with the saturated solution, however, usually leads to recrystallization of the solute and to a consequent return of the crystallinity and the measured solubility of the solid state to that of the pure, highly crystalline solid. 

The number of mobile holes is equal to the number of impurity Ni2+ ions, and so the fraction c in the Heikes equation is equal to x in LaNi,Coi -,(+. In accord with the theory, the Seebeck coefficient, a, is positive and greatest at low values of x and decreases as x increase (Fig. 1.12). Substituting a value of c = 0.02 into the equation yields a value of a = +335 pV K-1, in good agreement with the experimental value of 360 pV K-1 (Robert el al., 2006). Note that the above example also shows that an experimentally determined value of the Seebeck coefficient can be used to estimate the concentration of impurity defects in a doped oxide. 

The Schottky defect population in the electrolyte is rather too low for practical purposes. To overcome this problem the Lil is sometimes doped with Cal2. The extra I- ions extend the Lil structure, and the Ca2+ ions form substitutional impurity defects on sites normally reserved for Li+ ions. The consequence of this is that each Ca2+ ion in Lil will form one cation vacancy over and above those present due to Schottky defects in order to maintain charge neutrality. This can be written... 

In most ordinary solids, bulk diffusion is dominated by the impurity content, the number of impurity defects present. Any variation in D0 from one sample of a material to another is accounted for by the variation of the impurity content. However, the impurity concentration does not affect the activation energy of migration, Ea, so that Arrhenius plots for such crystals will consist of a series of parallel lines (Fig. 5.21a). The value of the preexponential factor D0 increases as the impurity content increases, in accord with Eq. (5.13). 

Pigments, minerals, gemstones, glasses, and many related materials are colored by impurity defects that absorb some of the incident white light, leaving a depleted spec-hum to color the solid. Colors in these materials are thus characterized by the absorption spectrum of the solid. Common inorganic colorants are the transition-metal and lanthanide metal ions. The colors ate characteristic of the ions themselves and are due... 

Besides REE, broad spectral bands characterize the luminescence of zircon. They are structureless down to 4.6 K, which makes difficult the correct interpretation of the nature of the luminescent centers. Different suppositions are made in previous studies and even the question about a yellow luminescence connection with intrinsic or impurity defect remains open. For example, the yellow band ( C-band ) was ascribed to SiO -defects (Votyakov et al. 1993 Krasnobayev et al. 1988) while the same emission ( band VII ) was explained by impurity luminescence, namely by Yb " " created by radioactive reduction of Yb " " (Kempe et al. 2000). 

It was thought for some time that central peaks were due to impurities, defects and other such extrinsic or intrinsic factors. A number of models and mechanisms based on entropy fluctuations, phonon density fluctuations, dielectric relaxation, molecular... 

Conversely, the presence of some metal ions of lower oxidation state in the metal ion sublattice requires vacant anion sites to balance the charge. In some cases, the charge imbalance is caused by ions of some other element or, rarely, by multiple valence of the anions. In any event, the empirical formula of a recognizable solid transition metal compound may be variable over a certain range, with nonintegral atomic proportions. Such non-stoichiometric compounds may be regarded as providing extreme examples of impurity defects. 

The identification of an impurity, defect, or impurity-defect complex by some particular technique must nearly always be accomplished in conjunction with doping experiments. Thus, the well-known, sharp, zero-phonon photoluminescence lines at 0.84 eV in GaAs are almost certainly associated with Cr, as established by Cr-doping experiments (Koschei et al., 1976). However, some care must be taken here. For example, a dominant electron trap (EL2) in -doped GaAs is probably not associated with O, according to recent experiments (Huber et al., 1979). Thus, the doping must be accompanied by a positive identification of the relevant impurity concentration, say by SSMS, or SIMS. These general considerations apply to all the techniques discussed below. 

Each listed type of randomization (orientional, hydrogen-bonding network, nuclear spin statistics, isotopes, impurities, defects, and others that could be cited) makes independent contributions to S0 0. Hence, it seems safe to conclude that no macroscopic sample of real substance that ever appeared on Earth satisfies S0 = 0, i.e., that every real substance represents an imperfect exception to the third law as commonly stated. 

Channeling studies of impurity-defect interactions in Si show that under helium ion bombardment the trapping efficiency of impurities for radiation-produced defects is very low, near 30 K (19). Vacancies are not mobile in Si below this temperature, whereas interstitials still are. This observation implies that the impurity-defect interactions involve vacancies. 

Intrinsic here refers to the conductivity of the ideal pure material free from impurities, defects, electrode effects etc., whereas extrinsic refers to the real situation. 

A word of caution the case of conjugated polymer films is generally identical to the case of condensed molecular solid films, as described above, but with occasional small differences. In general, the Fermi level is found to lie very near the centre of the energy gap, Eg. Small amounts of impurities, defects, or other charge donation (acceptor) species, however, can move the position of the Fermi... 

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