With the ability to modulate electronic
properties through molecular
doping coupled with ease in processability, semiconducting polymers
are at the forefront in enabling organic thermoelectric devices for
thermal energy management. In contrast to uniform thermoelectric material
properties, an alternative route focuses on functionally graded materials
(FGMs) where one spatially controls and optimizes transport properties
across the length of a thermoelectric material. While primarily studied
in the context of inorganic materials, the concept of FGMs for organic
thermoelectrics has not been explored. Herein, we introduce how molecular
doping of semiconducting polymers enables spatial compositional control
of thin-film FGMs. Specifically, we use sequential vapor doping of
poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) with the small molecule acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane
(F4TCNQ) to fabricate the simplest form of FGMsdouble-segmented
thin films. The two thin-film segments are of equal length (7.5 mm)
but each set to different doping levels. Our study focuses on understanding
the thermoelectric properties (Seebeck coefficient, α, and electronic
conductivity, σ) and structural properties (through X-ray scattering,
UV–vis–NIR spectroscopy, and Raman spectroscopy) within
and across the two segments. We observe the presence of a small diffuse
interfacial region of 0.5–1 mm between the two segments where
the doping level and transport properties vary continuously. Despite
the diffuse interface, the measured α across the two segments
is simply the average of α within each segment. Importantly,
this experimental result is consistent with reported mathematical
models describing the spatial average of α in graded
thermoelectric materials. Our results demonstrate the facile fabrication
and characterization of functionally graded organic thermoelectric
materials, providing guidelines for further development on more complex
FGMs.