Optimization
of carrier concentration plays an important role on
maximizing thermoelectric performance. Existing efforts mainly focus
on aliovalent doping, while intrinsic defects (e.g., vacancies) provide
extra possibilities. Thermoelectric GeTe intrinsically forms in off-stoichiometric
with Ge-vacancies and Ge-precipitates, leading to a hole concentration
significantly higher than required. In this work, Sb2Te3 having a smaller cation-to-anion ratio, is used as a solvend
to form solid solutions with GeTe for manipulating the vacancies.
This is enabled by the fact that each substitution of 3 Ge2+ by only 2 Sb3+ creates 1 Ge vacancy, because of the overall
1:1 cation-to-anion ratio of crystallographic sites in the structure
and by the charge neutrality. The increase in the overall Ge-vacancy
concentration facilitates Ge-precipitates to be dissolved into the
matrix for reducing the hole concentration. In a combination with
known reduction in hole concentration by Pb/Ge-substitution, a full
optimization on hole concentration is realized. In addition, the resultant
high-concentration point defects including both vacancies and substitutions
strongly scatter phonons and reduce the lattice thermal conductivity
to the amorphous limit. These enable a significantly improved thermoelectric
figure of merit at working temperatures of thermoelectric GeTe.
Hydrovoltaic technologies have been proposed in recent years to generate electricity by virtue of water interacting with nanostructured materials, such as monolayer graphene and graphene derivatives, as promising renewable energy...
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