Japan s major contribution to the development of wide bandgap semiconductor devices.
The discovery of blue emission from GaN p n junctions in was the major technological turning point during the development of wide bandgap emission devices with wide reaching scienti'c, industrial and social impli- tions. With references, figures and 21 tables, this book will serve as a one-stop source of knowledge on wide bandgap semiconductors and related optoelectronics devices.
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Wide Bandgap Semiconductors : Fundamental Properties and Modern Photonic and Electronic Devices
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The diamond structure is characterized by sp 3 hybrid orbitals which repel each other and are therefore directed from the central atom to the corners of a regular tetrahedron. The tetrahedra are arranged in layers, and if the position of the first layer perpendicular to the c axis is designated A , subsequent layers are stacked in the somewhat shifted positions B and C , resulting in a cubic stacking A — B — C — A — B — C see Fig.
In contrast, the orbitals in the stable modification of carbon, graphite, are sp 2 hybridized. The remaining non-hybridized delocalized electron is situated out of the carbon plane and is the origin of the almost metallic conductivity of graphite parallel to the basal carbon atom plane of its hexagonal structure. In lonsdaleite, the carbon tetrahedra show hexagonal stacking, A — B — A — B. In the schematic of Fig. The stacking of layers A — B — C from bottom to top in the diamond structure.
One atom of each layer is hatched for a better demonstration of the stacking sequence. The diamond-type elements of main group 4 show partial complete only in the case of Si—Ge mutual solubility. Typically, the solubility is larger possibly under non-equilibrium conditions for epitaxial layers.
The homogeneity range of the three solid phases in the phase diagram Fig. From the cubic diamond structure and the hexagonal lonsdaleite structure, binary or ternary compound structures, respectively, can be derived if the C atoms are substituted in an ordered manner by other atoms in such a way that the average of four electrons per atomic site is maintained; for an overview, see e.
The structures of diamond and lonsdaleite, and derived tetrahedrally bound compounds, are called adamantane types. It is obvious that the crystal symmetry drops with increasing chemical complexity. Only a few of these structure types, namely diamond, sphalerite and wurtzite, are found for wide-band gap semiconductors. Some others, such as kesterite and stannite, with narrow E g around 1. These AB compounds comprise alternating AB 4 or A 4 B , respectively tetrahedra which are linked through their corners.
Different stackings for the tetrahedron layers are observed, as for diamond and lonsdaleite. If diamond stacking is performed with the AB 4 tetrahedra, the atom sites are identical to those of diamond itself, with just the A and B atoms alternating. The structure remains cubic, but the symmetry is lowered to space group. In a similar way, lonsdaleite stacking of AB 4 tetrahedra also results in conservation of the atomic positions with alternating atom types.
The resulting wurtzite structure belongs to space group P 6 3 mc. The similarity of carbon and silicon is responsible for the low ionicity of SiC. In particular, a huge variety of stacking orders can be observed for this compound, called polytypes. Consequently, they can easily coexist or be transformed into each other, or switching between polytypes can occur during growth Rost et al. The polytypes are described by the Ramsdell notation, which is a number giving the period of the stacking followed by the letter H, C or R, indicating that the stacking symmetry is hexagonal, cubic or rhombohedral, respectively.
The second line reports the average thickness of a single layer, which does not differ much. SiC is mechanically hard, chemically inert, and can be integrated well into standard semiconductor production lines. The growth of single crystals is a challenge, as can be seen readily from the Si—C phase diagram in Fig. The large band gap, good carrier mobility and stability of SiC allow the production of electronic and optoelectronic devices with superior properties and a high breakdown field that are able to work even under harsh conditions.
It should be noted that SiC, under the name carborundum, is a mass product used e. Here, as for electronics, its high thermal conductivity is beneficial as it allows the removal of waste heat. SiC is the only tetrahedrally bound semiconductor that can be derived from diamond or lonsdaleite by replacing C alternately with C or Si, respectively.
If the structure is derived from diamond, one obtains the cubic zincblende sphalerite structure; if it is derived from lonsdaleite, the hexagonal wurtzite structure is obtained. It is notable that the names of both structure types are derived from zinc sulfide ZnS , which can be found as a natural mineral in both structure types. Other isoelectronic replacements, with identical structural features, can be obtained by replacing C group 4 of the periodic system alternately with elements from groups 3 and 5. Replacement with elements from main groups 2 and 6 results mainly in compounds with the sodium chloride structure, with a few exceptions such as the insulator BeO Austerman et al.
However, many subgroup elements also form bivalent ions: Those compounds with higher ionicity tend to crystallize in the wurtzite structure, and the higher ionicity goes along with a larger E g.
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For GaP, the optical transparency reaches the visible range and wafers are transparent to red light. Pure AlP, in contrast with other group 3 phosphides and arsenides, tends to hydrolyze with moisture to form poisonous phosphine gas PH 3 and is used as a pesticide. Gallium and indium phosphides, arsenides and, partially, antimonides for semiconductor applications are typically grown as bulk single crystals from the melt, either by crystallization inside a crucible from the bottom to the top Bridgman; vertical gradient freeze or VGF or by pulling Czochralski.
Arsenides and more so phosphides tend to have a large arsenic or phosphorus vapour pressure up to several tens of bar at their melting points. Among the group 3 nitrides, BN has not yet reached its full potential. For the other group 3 elements, the affinity to nitrogen decreases in the order Al—Ga—In, which results in decomposition of the nitrides upon heating below their melting points.
In fact, InN is so far only relevant as an admixture to Al,Ga,In N mixed crystals because the growth of single crystals is difficult. The stability of AlN is shown in the T —log[ p ] phase diagram in Fig. Calculated using FactSage 6. For GaN the establishment of suitable growth conditions is more difficult, because gallium in contrast with aluminium does not evaporate sufficiently for sublimation growth. In fact, Ga is the chemical element with the broadest range of liquid-phase stability under ambient pressure: Other technologies for the growth of bulk GaN rely on chemical transport of the gallium species: However, some drawbacks have to be taken into account: Crystalline GaN is then deposited either by the thermal decomposition of GaCN or by a reaction that is analogous to that of the common HVPE growth technique given above.
Meanwhile, remarkable technological progress has been achieved, and now Al,Ga,In N-based devices are the basis for solid-state lighting applications. Because GaN and AlN substrates are still scarce and expensive, homoepitaxy plays no significant role and is still used mainly for basic research Funato et al. LiAlO 2 and LiGaO 2 are interesting alternatives because their epitaxial misfit is much lower compared with e.