Surface Chemical Tuning of Phonon and Electron Transport in Free-Standing Silicon Nanowire Arrays.

We report electronic and phononic transport measurements of monocrystalline batch-fabricated silicon nanowire (SiNW) arrays functionalized with different surface chemistries. We find that hydrogen-terminated SiNWs prepared by vapor HF etching of native-oxide-covered devices show increased electrical conductivity but decreased thermal conductivity. We used the kinetic Monte Carlo method to solve the Boltzmann transport equation and also numerically examine the effect of phonon boundary scattering. Surface transfer doping of the SiNWs by cobaltocene or decamethylcobaltocene drastically improves the electrical conductivity by 2 to 4 orders of magnitude without affecting the thermal conductivity. The results showcase surface chemical control of nanomaterials as a potent pathway that can complement device miniaturization efforts in the quest for more efficient thermoelectric materials and devices.