Synthesis and Structural and Optical Properties of Ga(As 1-x P x )Ge 3 and (GaP) y Ge 5-2y Semiconductors Using Interface-Engineered Group IV Platforms.

Epitaxial synthesis of Ga(As1-x Px )Ge3 alloys on Si(100) substrates is demonstrated using chemical vapor deposition reactions of [D2 GaN(CH3 )2 ]2 with P(GeH3 )3 and As(GeH3 )3 precursors. These compounds are chosen to promote the formation of GaAsGe3 and GaPGe3 building blocks which interlink to produce the desired crystalline product. Ge-rich (GaP)y Ge5-2y analogues have also been grown with tunable Ge contents up to 90% by reactions of P(GeH3 )3 with [D2 GaN(CH3 )2 ]2 under similar deposition protocols. In both cases, the crystal growth utilized Ge1-x Six buffer layers whose lattice constants were specifically tuned as a function of composition to allow perfect lattice matching with the target epilayers. This approach yielded single-phase materials with excellent crystallinity devoid of mismatch-induced dislocations. The lattice parameters of Ga(As1-x Px )Ge3 interpolated among the Ge, GaAs, and GaP end members, corroborating the Rutherford backscattering measurements of the P/As ratio. A small deviation from the Vegard's law that depends on the As/P ratio was observed and corroborated by ab initio calculations. Raman scattering shows evidence for the existence of Ga-As and Ga-P bonds in the Ge matrix. The As-rich samples exhibited photoluminescence with wavelengths similar to those observed for pure GaAsGe3 , indicating that the emission profile does not change in any measurable manner by replacing As by P over a broad range up to x = 0.2. Furthermore, the photoluminescence (PL) data suggested a large negative bowing of the band gap as expected on account of a strong valence band localization on the As atoms. Spectroscopic ellipsometry measurements of the dielectric function revealed a distinct direct gap transition that closely matches the PL emission energy. These measurements also showed that the absorption coefficients can be systematically tuned as a function of composition, indicating possible applications of the new materials in optoelectronics, including photovoltaics.