The use of surfactants to control specific aspects of the vapor-phase epitaxial growth process is beginning to be studied for both the elemental and III/V semiconductors. To date, most reported surfactant effects for semiconductors relate to the morphology of the growing films. However, semiconductor alloys with CuPt ordering exhibit much more dramatic effects. The change in the CuPt order parameter induced by the surfactant translates into a marked change in the band-gap energy. Previous work concentrated on the effects of the donor tellurium. Te is less than ideal as a surfactant, since the change in band-gap energy is coupled to a large change in the conductivity. This letter presents the results of a study of the effects of an isoelectronic surfactant on the ordering process in GaInP. Sb has been found to act as a surfactant during organometallic vapor-phase epitaxial growth. At an estimated Sb concentration in the solid of 1 10 ✁ 4 , order is eliminated, as indicated by the band-gap energy. Surface photoabsorption ✂ SPA✄ data indicate that the effect is due to a change in the surface reconstruction. Adding Sb leads to attenuation of the peak at 400 nm in the SPA spectrum associated with ☎ 1 10✆ P dimers. The addition of Sb during the growth cycle has been used to produce a heterostructure with a 135 meV band-gap difference between two layers with the same solid composition.

A surfactant is used to induce an ordered structure in an epitaxial layer. The addition of small amounts of triethylantimony during the organometallic vapor phase epitaxy growth of GaInP on (001) GaAs substrates is shown to remove CuPt ordering with a resultant increase in band gap energy. Increasing the concentration of Sb in the vapor beyond a critical Sb to P ratio [Sb/P(v)] of 4×10−4 gives a reversal of this behavior. The band gap energy is observed to decrease by 50 meV at a concentration of Sb/P(v)=1.6×10−3, coincident with the formation of an ordered phase with a period triple the normal lattice spacing along the [111] and [1̄1̄1] directions. The formation of this new ordered structure is believed to be related to high concentrations of Sb on the surface, which leads to a change in the surface reconstruction from (2×4)-like to (2×3)-like, as indicated by surface photoabsorption performed in situ.

GaAs:N is an interesting material for many devices due to its unique compositional variation of band gap. Small amounts of N lead to a strong decrease in band gap energy as well as lattice constant. The further addition of In or Sb leads to quaternary alloys with band gap energies below 1.4 eV lattice matched to GaAs. One drawback of these alloys is the low solubility of N in GaAs. Some success has been obtained using low growth temperatures and V/III ratios during organometallic vapor phase epitaxy to kinetically limit phase separation. This article describes mechanisms for N incorporation into the GaAs crystal during growth and shows how surfactants like Sb, Bi, and Tl, as well as B, affect N incorporation. A decrease of the N content in GaAs was found for Sb, Bi, and Tl, which can be explained using a simple Langmuir model with competitive adsorption. The surface morphology of the epitaxial layers and the influence of surfactants was analyzed using atomic force microscopy.

Recently, the addition of the isoelectronic surfactant Sb during organometallic vapor phase epitaxy (OMVPE) of GaInP was shown to eliminate ordering, resulting in a significant change in the band gap energy. These results suggest that surfactants added during growth could have profound affects on other important properties of semiconductors, such as doping. This letter presents the results of a recent study on the effects of the isoelectronic surfactant Sb on doping in GaAs. The addition of a small amount of triethylantimony during OMVPE of GaAs is found, using secondary ion mass spectroscopy analysis, to increase the Zn doping concentration from <6×1018 atoms/cm3 to 9×1018 atoms/cm3, a factor of 1.6. The amount of antimony introduced into the solid is only 2–3×1017 atoms/cm3. The addition of Sb also increases the impurity concentration of In in GaAs, but does not affect the concentration of Te or P.

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