CuPt type ordering, which consists of a monolayer compositional modulation along one of the 4 〈111〉 directions in the lattice, was studied using transmission electron microscopy for GaAs1−xPx with values of x extending from 0.25 to 0.85. The samples were grown by organometallic vapor phase epitaxy on nominal (001) GaAs substrates that were misoriented by varying amounts in three directions. No CuPt type ordering was observed for GaAs1−xPx with x ≤0.35, while ordering was found to occur for 0.4≤x≤0.85. The direction of substrate misorientation has a major effect on the determination of which of the four possible CuPt variants are formed for 0.4≤x≤0.85. Two variants, with ordering on the (1̄11) and (11̄1) planes, appear for epilayers grown on substrates oriented exactly on the (001) plane and for substrates misoriented by 6° towards the [110] direction. Only one variant, with ordering on the (1̄11) plane, appears for epilayers grown on substrates misoriented by 6° towards [1̄10]. These ordering-induced spots observed in transmission electron diffraction (TED) patterns for GaAsP occur only for the [110] cross section. From TED studies of GaInP grown on similar substrates, we conclude that the CuPt variants in GaAsP are exactly the same as for GaInP. Further evidence supporting this conclusion was obtained by growing first a layer of GaInP followed by a layer of GaAsP. High-resolution dark field electron micrographs show domains of the same variants in both layers. A mechanism describing the formation of the specific ordered variant for both GaAsP and GaInP is proposed. From studies of ordering in a strain-layer superlattice, the strain due to lattice mismatch was found to play no significant role in the propagation of ordered domains. Microtwins, also generated due to lattice mismatch, can act as domain boundaries and prevent the propagation of the ordered domains.
GaAs1−xPx with 0.4≤x≤0.85 forms the CuPt ordered structure during organometallic vapor phase epitaxy (OMVPE). Only the (1̄11) and (11̄1) variants are observed for growth on (001)-oriented substrates. The mechanism by which ordering occurs is only now being discovered. Total energy calculations, including the effects of surface reconstruction, indicate that the phenomenon can be explained purely on the basis of energy considerations. Indirect evidence indicates that kinetic factors, including processes occurring at steps propagating across the surface in the two-dimensional growth mode, control ordering. In this work, GaAs1−xPx layers have been grown by OMVPE on (001)-oriented GaAs0.6P0.4‘‘substrates.’’ In order to examine the effects of surface kinetic factors, the substrates were first patterned with [110]-oriented grooves 5 μm wide and a fraction of a micron deep. The groove is used to provide a source of steps moving in opposite directions from the two edges. Transmission electron diffraction reveals the formation of large domains of the two variants that meet in the center of the groove. A surprising feature is the presence of a region in the groove with absolutely no ordering. Tracing the surface shape during growth using a superlattice structure indicates that the disordered region is due to growth on {511} facets. The domains formed after the groove is filled are very large, several square microns in cross-sectional area and extending along the entire length of the groove. These results demonstrate that natural ordering in GaAsP, an alloy with mixing on the group V sublattice, can be controlled by regulating the propagation of steps during growth, exactly as for GaInP where mixing is on the group III sublattice.
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