Practical routes to (SiH₃)₃P: Applications in group IV semiconductor activation and in group III-V molecular synthesis

The (SiH₃)₃P hydride is introduced as a practical source for n-doping of group iv semiconductors and as a highly-reactive delivery agent of -(SiH₃)₂P functionalities in exploratory synthesis. In contrast to earlier methods, the compound is produced here in high purity quantitative yields via a new single-step method based on reactions of SiH₃Br and (Me₃Sn)₃P, circumventing the need for toxic and unstable starting materials. As an initial demonstration of its utility we synthesized monosubstituted Me₂M-P(SiH₃) ₂ (M = Al, Ga, In) derivatives of Me₃M containing the (SiH₃)₂P ligand for the first time, in analogy to the known Me₂M-P(SiMe₃)₂ counterparts. A dimeric structure of Me₂M-P(SiH₃)₂ is proposed on the basis of spectroscopic characterizations and quantum chemical simulations. Next, in the context of materials synthesis, the (SiH₃)₃P compound was used to dope germanium for the first time by building a prototype p⁺⁺Si(100)/i-Ge/n-Ge photodiode structure. The resultant n-type Ge layers contained active carrier concentrations of 3-4 × 10¹⁹ atoms cm^-3 as determined by spectroscopic ellipsometry and confirmed by SIMS. Strain analysis using high resolution XRD yielded a Si content of 4 × 10²⁰ atoms cm^-3 in agreement with SIMS and within the range expected for incorporating Si₃P type units into the diamond cubic Ge matrix. Extensive characterizations for structure, morphology and crystallinity indicate that the Si co-dopant plays essentially a passive role and does not compromise the device quality of the host material nor does it fundamentally alter its optical properties.