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1 A Crystal

Crystallography is based on a specic symmetry which is called translational symmetry. The exact meaning of translational symmetry will be clearer when reading this book. On an intuitive level we can dene a crystal as a 3D object densely built of repeating structural units located at xed distances from their neighbors, the distances being unchanged across the crystal volume. This picture is a result of scientic developments over hundreds of years. In fact, attempts to understand the internal structure of materials had been undertaken already in ancient times. Most renowned is the speculative atomic theory of ancient Greeks (primarily by Leucippus and Democritus). At the end of the middle ages and, especially, during the Renaissance period, people began to recognize the importance of measurements for establishing scientic concepts. Perhaps Dutch jewelers were the rst to understand that diamond stone is built differently from a piece of amber. However, the rst quantitative results are dated by 1669, when Danish professor of anatomy Nicolas Stenon, the court physician of Duke of Toscana, published a paper, in which he established the rst law of crystallography the law of constant angles. While crystals of the same material can differ by their external shape and size, the angles between the corresponding crystal faces are always identical. In his study, Stenon had measured the angles between faces forming the habits (typical shapes) of large natural crystals of quartz (SiO2) and hematite (Fe2O3). The next important step was accomplished only in 1784, by French mineralogist Ren Ha y, who established the second law of crystallography the law of rational e u parameters. According to Ha y, if certain edges of a crystal are taken as the axes of u coordinate system, than the ratios of segments cut by two dissimilar crystal faces on any axis are always found to be rational fractions. In other words, the segments mentioned can be expressed as integer numbers of some elementary lengths. In fact, the exact meaning of this law was understood later in the context of so-called Miller indexes (see Chapter 3), which were introduced only in 1839. Anyway, it was a great discovery, since on that basis one can rmly conclude that the crystal consists of some repeating blocks, the integer number of which within crystalline specimens provides

Basic Concepts of Crystallography, Emil Zolotoyabko. 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2011 by Wiley-VCH Verlag GmbH & Co. KGaA.

j 1 A Crystal
the law of rational parameters. The presence of elementary blocks assembled without voids assure 3D periodicity on a scale dictated by the block size. Ha y assumed that u elementary blocks, which form crystals, are small polyhedrons. Therefore, long before modern powerful methods of structural analysis, by measuring the crystal habits only, the spatial periodicity of crystalline structures was deduced. Nowadays, by using high-resolution transmission electron microscopy or scanning tunneling microscopy, the periodic atomic networks within crystals or on crystal surface can be directly visualized (see Figures 1.1 and 1.2, respectively). In fact, it is amazing that such giant numbers of atoms or molecules ($1023) are disposed at equal distances from each other, and it is worth discussing very briey the reasons behind that. Strictly speaking we have no comprehensive quantitative description of such cooperative phenomenon. We know only that the interatomic potential consists of two terms of opposite signs reecting short-distance repulsion between ion cages and long-distance attraction between ions via electron glue. Competition between these two contributions provides the minimum of the potential at some xed distance, rd (see Figure 1.3), which could be considered as the interatomic distance in a crystal. However, crystal formation is a cooperative action of billions and billions of atoms and we are still far from being able to calculate these collective effects with high enough accuracy. Nevertheless, thermodynamics predicts that, at least at zero absolute temperature, T 0, the structurally ordered state is most favorable. According to the third law of thermodynamics, the entropy, S, of the system tends to zero, when T ! 0. In turn,

Figure 1.1 High-resolution transmission electron microscopy image of atomic columns in the InAs/GaSb superlattice.

1 A Crystal

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Figure 1.2 Scanning tunneling microscopy image (29.7 29.7 nm) of the periodically arranged atomic rows on the cleavage surface of the InAs/GaSb superlattice.

Repulsion

Potential

rd

Attraction Distance, r
Figure 1.3 Typical behavior of interatomic potential as a function of the interatomic distance, r. Sharp ascent left-side from the equilibrium point, rd, is due to repulsive forces between ions, while attractive forces result in the tile slowly approaching zero potential at large distances, r ) rd.

j 1 A Crystal
entropy, S, is related to the number of possible system congurations, N, by the Boltzmann equation:
S k ln N 1:1

where k is the Boltzmann constant. It follows from Equation 1.1 that in order to have S 0 at T 0, the value of N should be one, that is, the single (unique) conguration of the system is realized. It is evident that this corresponds to the ordered state, since any deviation from order towards disordered state could be realized in many equivalent ways. In fact, if we have a number of spatially ordered atoms in our system, tiny shift of each of them means certain disorder and thus the number of disordered congurations grows rapidly with the number of atoms involved. If temperature T > 0, thermodynamics allows different congurations of the system to exist, including disordered ones. Practically, we know that at room temperature some solid materials exist in the amorphous (i.e. structurally disordered) form, which is possible, at least, from the entropy point of view. However, the amorphous form of a material is the exception rather than the rule, since it is assumed that even at nite temperature there are crystalline forms with lower free energy. If so, the amorphous state is always metastable, that is, it seemingly exists because of the insignicant diffusion rates or due to some stabilizing factors, such as for example, a high concentration of impurity atoms or other lattice defects, inhomogeneous strain elds, and so on. Nonetheless, most solid materials are crystals, and we begin by describing their symmetry properties.