Theory of diffusion controlled reactions of point defects in metals

Author(s):  
K. Schröder
1995 ◽  
Vol 378 ◽  
Author(s):  
S. Pizzini ◽  
S. Binetti ◽  
M. Acciarri

AbstractThe chemistry of the interactions between point defects and impurities is discussed by considering first the general thermodynamic and kinetic aspects of these reactions, deserving major attention to the identity of of the stable chemical species eventually formed and to the boundary conditions for diffusion controlled and reaction controlled interaction processes.The second part of the paper is instead dedicated to the analysis of the chemistry of carbon, oxygen, hydrogen and point defects in silicon, which is a system of major technological interest.We postulate that at low enough temperatures, when homogeneous nucleation processes are slow, spinodal decomposition assists oxygen aggregation phenomena. We postulate, also, on the basis of the existing knowledge, that carbon and hydrogen favour alternative reaction paths for oxygen in the due of clustering processes and discuss the hydrogen-enhanced oxygen diffusivity in the frame of a conventional trapping model.


Author(s):  
W. T. Donlon ◽  
S. Shinozaki ◽  
E. M. Logothetis ◽  
W. Kaizer

Since point defects have a limited solubility in the rutile (TiO2) lattice, small deviations from stoichiometry are known to produce crystallographic shear (CS) planes which accomodate local variations in composition. The material used in this study was porous polycrystalline TiO2 (60% dense), in the form of 3mm. diameter disks, 1mm thick. Samples were mechanically polished, ion-milled by conventional techniques, and initially examined with the use of a Siemens EM102. The electron transparent thin foils were then heat-treated under controlled atmospheres of CO/CO2 and H2 and reexamined in the same manner.The “as-received” material contained mostly TiO2 grains (∼5μm diameter) which had no extended defects. Several grains however, aid exhibit a structure similar to micro-twinned grains observed in reduced rutile. Lattice fringe images (Fig. 1) of these grains reveal that the adjoining layers are not simply twin related variants of a single TinO2n-1 compound. Rather these layers (100 - 250 Å wide) are alternately comprised of stoichiometric TiO2 (rutile) and reduced TiO2 in the form of Ti8O15, with the Ti8O15 layers on either side of the TiO2 being twin related.


Author(s):  
William Krakow

Tilted beam dark-field microscopy has been applied to atomic structure determination in perfect crystals, several synthesized molecules with heavy atcm markers and in the study of displaced atoms in crystals. Interpretation of this information in terms of atom positions and atom correlations is not straightforward. Therefore, calculated dark-field images can be an invaluable aid in image interpretation.


Author(s):  
John A. Sutliff

Near-eutectic Pb-Sn alloys are important solders used by the electronics industry. In these solders, the eutectic mixture, which solidifies last, is the important microstructural consituent. The orientation relation (OR) between the eutectic phases has previously been determined for directionally solidified (DS) eutectic alloys using x-ray diffraction or electron chanelling techniques. In the present investigation the microstructure of a conventionally cast, hyper-eutectic Pb-Sn alloy was examined by transmission electron microscopy (TEM) and the OR between the eutectic phases was determined by electron diffraction. Precipitates of Sn in Pb were also observed and the OR determined. The same OR was found in both the eutectic and precipitation reacted materials. While the precipitation of Sn in Pb was previously shown to occur by a discontinuous precipitation reaction,3 the present work confirms a recent finding that volume diffusion controlled precipitation can also occur.Samples that are representative of the solder's cast microstructure are difficult to prepare for TEM because the alloy is multiphase and the phases are soft.


Author(s):  
Kenneth R. Lawless

One of the most important applications of the electron microscope in recent years has been to the observation of defects in crystals. Replica techniques have been widely utilized for many years for the observation of surface defects, but more recently the most striking use of the electron microscope has been for the direct observation of internal defects in crystals, utilizing the transmission of electrons through thin samples.Defects in crystals may be classified basically as point defects, line defects, and planar defects, all of which play an important role in determining the physical or chemical properties of a material. Point defects are of two types, either vacancies where individual atoms are missing from lattice sites, or interstitials where an atom is situated in between normal lattice sites. The so-called point defects most commonly observed are actually aggregates of either vacancies or interstitials. Details of crystal defects of this type are considered in the special session on “Irradiation Effects in Materials” and will not be considered in detail in this session.


Author(s):  
Byung-Teak Lee

Grown-in dislocations in GaAs have been a major obstacle in utilizing this material for the potential electronic devices. Although it has been proposed in many reports that supersaturation of point defects can generate dislocation loops in growing crystals and can be a main formation mechanism of grown-in dislocations, there are very few reports on either the observation or the structural analysis of the stoichiometry-generated loops. In this work, dislocation loops in an arsenic-rich GaAs crystal have been studied by transmission electron microscopy.The single crystal with high arsenic concentration was grown using the Horizontal Bridgman method. The arsenic source temperature during the crystal growth was about 630°C whereas 617±1°C is normally believed to be optimum one to grow a stoichiometric compound. Samples with various orientations were prepared either by chemical thinning or ion milling and examined in both a JEOL JEM 200CX and a Siemens Elmiskop 102.


Author(s):  
M. Awaji

It is necessary to improve the resolution, brightness and signal-to-noise ratio(s/n) for the detection and identification of point defects in crystals. In order to observe point defects, multi-beam dark-field imaging is one of the useful methods. Though this method can improve resolution and brightness compared with dark-field imaging by diffuse scattering, the problem of s/n still exists. In order to improve the exposure time due to the low intensity of the dark-field image and the low resolution, we discuss in this paper the bright-field high-resolution image and the corresponding subtracted image with reference to a changing noise level, and examine the possibility for in-situ observation, identification and detection of the movement of a point defect produced in the early stage of damage process by high energy electron bombardment.The high-resolution image contrast of a silicon single crystal in the [10] orientation containing a triple divacancy cluster is calculated using the Cowley-Moodie dynamical theory and for a changing gaussian noise level. This divacancy model was deduced from experimental results obtained by electron spin resonance. The calculation condition was for the lMeV Berkeley ARM operated at 800KeV.


Author(s):  
S. R. Singh ◽  
H. J. Fan ◽  
L. D. Marks

Since the original observation that the surfaces of materials undergo radiation damage in the electron microscope similar to that observed by more conventional surface science techniques there has been substantial interest in understanding these phenomena in more detail; for a review see. For instance, surface damage in a microscope mimics damage in the space environment due to the solar wind and electron beam lithographic operations.However, purely qualitative experiments that have been done in the past are inadequate. In addition, many experiments performed in conventional microscopes may be inaccurate. What is needed is careful quantitative analysis including comparisons of the behavior in UHV versus that in a conventional microscope. In this paper we will present results of quantitative analysis which clearly demonstrate that the phenomena of importance are diffusion controlled; more detailed presentations of the data have been published elsewhere.As an illustration of the results, Figure 1 shows a plot of the shrinkage of a single, roughly spherical particle of WO3 versus time (dose) driven by oxygen desorption from the surface.


Author(s):  
L. J. Sykes ◽  
J. J. Hren

In electron microscope studies of crystalline solids there is a broad class of very small objects which are imaged primarily by strain contrast. Typical examples include: dislocation loops, precipitates, stacking fault tetrahedra and voids. Such objects are very difficult to identify and measure because of the sensitivity of their image to a host of variables and a similarity in their images. A number of attempts have been made to publish contrast rules to help the microscopist sort out certain subclasses of such defects. For example, Ashby and Brown (1963) described semi-quantitative rules to understand small precipitates. Eyre et al. (1979) published a catalog of images for BCC dislocation loops. Katerbau (1976) described an analytical expression to help understand contrast from small defects. There are other publications as well.


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