RESEARCH ARTICLE

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Highly Conductive n-Type Polymer Fibers from the

Wet-Spinning of n-Doped PBDF and Their Application in
Thermoelectric Textiles
Ruben Sarabia-Riquelme,* Leah E. Noble, Paula Alarcon Espejo, Zhifan Ke,
Kenneth R. Graham, Jianguo Mei, Alexandra F. Paterson, and Matthew C. Weisenberger

1. Introduction
The field of electronic textiles currently lacks n-type polymer fibers that can
complement the more established p-type polymer fibers. Here, a highly Electronic textiles are textiles that can per-
conductive n-type polymer fiber is obtained via wet-spinning of n-doped form a wide range of functions such as
health monitoring, motion sensing, com-
poly(3,7-dihydrobenzo[1,2-b:4,5-b’]difuran-2,6-dione) (n-PBDF). The electrical puting, communicating, and energy stor-
conductivity of the fibers increases from 1000 to 1600 S cm−1 with increased age and harvesting, among others. Practi-
draw during processing and correlates well with Young’s modulus. Wide-angle cally all commercial electronic textiles take
X-ray scattering reveals the existence of a bimodal orientation of the polymer advantage of the miniaturization of tradi-
chains, favoring parallel alignment to the fiber axis with increased draw. After tional electronics and circuits to embed
them directly onto the textile.[1,2] However,
14 d in 80% humid air, fiber conductivity stabilizes maintaining 81% of the
even miniaturized, electronic components,
initial conductivity. Although the electrical conductivity drops slightly over such as wires, batteries, LEDs, antennas,
time, the Seebeck coefficient increases, resulting in the highest thermoelectric chips, etc., do not offer the same level of
power factor being measured at 91 μW m−1 K−2 for the most drawn fiber 14 d comfort and breathability found in tradi-
after its fabrication. A proof-of-concept two-couple thermoelectric textile is tional textiles. To solve this issue, research
crafted by embroidering bundles of n-type PBDF fibers and p-type PEDOT:PSS in the electronic textile field has shifted to
develop electrically conducting and func-
fibers. The device generates 2.40 nW at a 22 °C temperature gradient. This tional fibers that can be patterned into or
work represents the initial steps and a crucial advancement toward fabricating onto textiles by traditional weaving, sewing,
high-performance n-type polymer fibers that can complement their p-type knitting, embroidery, and other textile-
counterparts to close the existing performance gap. forming techniques.[3,4] These functional
fibers have the flexibility and conformabil-
ity of traditional fibers while also acting
as the active material, bridging together
the fields of textiles and electronics.[5,6]
Conjugated polymers offer very attractive characteristics to be-
R. Sarabia-Riquelme, L. E. Noble, M. C. Weisenberger come the material from which such functional fibers are made.
Center for Applied Energy Research They have good mechanical properties and flexibility, are made
University of Kentucky
Lexington, KY 40506, USA
of earth-abundant, inexpensive elements, and can be processed
E-mail: [email protected] from solution or melt allowing for low-cost large-scale flow pro-
P. Alarcon Espejo, A. F. Paterson cessing methods. Indeed, the most common method to fabricate
Department of Chemical and Materials Engineering electrical conducting and functional polymeric fibers involves
Center for Applied Energy Research the deposition of the conducting polymer onto an inert fiber
University of Kentucky support using techniques such as in-situ polymerization[7,8] or
Lexington, KY 40506, USA
dyeing.[9–12] In these fibers, the insulating support fiber acts as
Z. Ke, J. Mei
Department of Chemistry a load-bearing substrate while the conjugated polymer coating
Purdue University provides electrical functionality. However, the volume mismatch
West Lafayette, IN 47907, USA between the thin active layer compared to the insulating sup-
K. R. Graham port fiber typically renders low bulk electrical conductivities, of-
Department of Chemistry ten lower than 10 S cm−1 , which limits their applications.[5]
University of Kentucky
Lexington, KY 40506, USA
One of the key breakthroughs in textile history was the
fabrication of man-made or synthetic fibers that started with
The ORCID identification number(s) for the author(s) of this article DuPont’s nylon in 1938 and led to a revolution in fashion and
can be found under https://doi.org/10.1002/adfm.202311379 textiles. Similarly, the direct fabrication of pure conducting
DOI: 10.1002/adfm.202311379 polymer fibers, avoiding altogether the need for an inert support,

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is an intriguing endeavor. The direct spinning of conducting the authors’ knowledge, this is the first time that an n-type poly-
polymers into fibers has been reported by several authors. mer fiber has been obtained by directly spinning a pure n-type
Polyaniline,[13–16] poly(3-alkyl-thiophenes),[17–19] polypyrrole,[20] polymer. Moreover, the fibers show high electrical conductivity
and poly(3,4-ethyelendioxythiophene):poly(styrene sulfonate) in the range from 1000 to 1600 S cm−1 depending on the total
(PEDOT:PSS)[21–27] have all been spun into fibers using either draw applied during processing. These levels of electrical con-
melt-spinning or wet-spinning methods. Among these, PE- ductivity are significantly higher than common n-type polymer
DOT:PSS fibers have shown the most promise with electrical materials and already rival those of PEDOT:PSS fibers despite the
conductivities over 4000 S cm−1 and excellent mechanical processing still being in its infancy. The Young’s modulus of the
properties.[26,27] However, all the above-mentioned fibers are fibers also increases from 9.7 to 19.5 GPa with increasing draw
p-type or, in other words, they exhibit hole-dominant charge and a good correlation is found between the Young’s modulus
transport. Nevertheless, both hole-transporting and electron- and the electrical conductivity. However, the electrical conductiv-
transporting fibers are required to fabricate high-performance ity of the fibers is found to degrade over time losing 50% or more
opto- and (bio-)electronic textile devices.[28] For instance, n-type of its value after 2 weeks. Nevertheless, the conductivity can be
fiber materials are needed to fabricate complementary logic stabilized if the fibers are stored in dry nitrogen or a high relative
circuits with well-matched p-type fibers, in fiber-based organic humidity environment. The Seebeck coefficient of the fibers is
electrochemical transistors (OECTs).[28–30] Additionally, organic found to be independent of draw and increases in absolute value
thermoelectric textiles hold great promise as power sources for over time from −19 μV K−1 at day 0 to −33 μV K−1 after 14 d.
low-consuming electronic textile sensors and devices, however, Interestingly, despite the drop in conductivity, the highest power
a high-performance n-type counterpart to the p-type material is factor is found at ≈91 μW m−1 K−2 for the most drawn fiber af-
also needed.[29,31] ter 14 d since fabrication. We then hand-sewn two bundles of the
Most n-type fibers reported in the literature are fabricated n-type PBDF fibers and two bundles of p-type PEDOT:PSS fibers
from nanocarbon materials such as fullerenes or carbon nan- into a cotton cloth to fabricate a small two-couple thermoelec-
otubes, either by coating existing insulating fibers[32,33] or by tric textile device that could generate 2.40 nW of power at a 22 °C
spinning carbon nanotube fibers followed by treatment with temperature gradient. We believe these results represent a signif-
an n-type dopant.[34–37] However, there are very few reports icant step forward in the field of electronic fibers and a stepping
demonstrating n-type polymer-based fibers. Canesi et al.[38] elec- stone to realizing electronic textiles from complementary high-
trospun blends of poly([N,N′-bis(2-octyl-dodecyl)-naphthalene- performance p-type and n-type polymeric fibers.
1,4,5,8-bis(dicarboximide)−2,6-diyl]-alt-5,5′-(2,2′-bithiophene))
(P(NDI2OD-T2)) and poly(ethyleneoxide) (PEO) where PEO 2. Results and Discussion
acted as the carrier polymer during the electrospinning process.
The electrospun fibers were used as the channel in field effect Figure 1a shows a schematic of the continuous wet-spinning pro-
transistors with mobility values ranging from 0.05 to 0.09 cm2 cess utilized in this work. A solution containing ≈0.85 wt% n-
V−1 s−1 . More recently, Darabi et al.[31] spray-coated regenerated PBDF in dimethyl sulfoxide (DMSO) was loaded into a plastic
cellulose yarns with an n-type conducting polymer-based ink syringe and extruded through a 5 μm filter and a 100 μm capil-
composed of poly(benzimidazobenzophenanthroline) (BBL) lary spinneret at a constant flow rate of 0.25 mL h−1 into a co-
and poly(ethyleneimine) (PEI). These BBL:PEI-coated cellulose agulation bath containing isopropanol at room temperature. The
yarns showed a bulk electrical conductivity of 0.008 S cm−1 n-PBDF solution rapidly coagulated in the isopropanol bath and
and a thermoelectric power factor of 0.4 μW m−1 K−2 and were could be continuously collected into a rotating roller. Due to the
paired with PEDOT:PSS-coated cellulose yarns to demonstrate a high surface area to volume ratio of the fibers, isopropanol evap-
working thermoelectric textile. orated quickly from the fibers. Typically, the rotating roller was
The main factor contributing to the lack of n-type polymer situated at about 15 cm from the point of filament emergence
fibers has been the limited availability of environmentally sta- (allowing for 7 to 16 s of travel time in air depending on draw)
ble and solution-processable n-type conducting polymers.[28,38] to ensure drying. We did not observe any sticking of the fibers
Nevertheless, over the last few years, there have been significant to the spool or to themselves, consistent with them being dry.
breakthroughs in the field of n-type polymer synthesis that have Water and acetone were also tested as coagulants; however, they
led to relatively environmentally stable polymers with properties did not coagulate the n-PBDF solution. It was found that both
rivaling those of the benchmark PEDOT:PSS.[28,39–42] Particularly, water and acetone acted as solvents to the n-PBDF, and there-
thin films of n-doped poly(3,7-dihydrobenzo[1,2-b:4,5-b’]difuran- fore do not induce the phase inversion of the n-PBDF from so-
2,6-dione) (n-PBDF) have been reported with conductivities of lution. The linear speed of the rotating roller was varied to col-
up to 2000 S cm−1 , and up to 6000 S cm−1 , with Hall mobilities lect fibers at 1.05, 1.50, 2.00, and 2.50 total draws, where the total
around 1.01 and 0.5 cm2 V−1 s−1 , respectively, and Seebeck coef- draw was calculated as the ratio between the linear speed of the
ficient of −21.0 μV K−1 .[40,41] Moreover, n-PBDF can be processed rotating roller and the velocity of the dope exiting the spinneret.
from solution and it has been reported to have remarkable wa- Collecting fibers at 3.00 total draw was also attempted but it led to
ter and environmental stability since it has a low LUMO level of frequent fiber breakage indicating that 3.00 was over the critical
−5.1 eV in its neutral state.[41] draw ratio for this polymer solution. However, utilizing this pro-
Motivated by this breakthrough in thin films, we embarked on cess at 2.50 total draw or below, a virtually infinite length of fiber
studying the wet-spinning of pure n-PBDF into fibers. We re- can be continuously collected. The linear density of the fibers de-
port the successful fabrication of n-type n-PBDF fibers by wet- creased with increasing draw (Figure 1b) closely following the
spinning utilizing an isopropanol coagulation bath. To the best of theoretical values obtained from a mass balance (see Supporting

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Figure 1. a) Schematic of the wet-spinning process used to fabricate the n-PBDF fibers. b) Linear density of fibers fabricated at different total draw ratios.
The dashed line represents the estimated linear density curve from a mass balance to the system (see Supporting Information). c) Average effective
diameters and circularity of fibers fabricated at different total draw ratios. d) SEM image of the surface of a n-PBDF fiber spun at 2.50 total draw. The
inset zooms in to better observe the grooves and ridges present on the surface of the fibers. e) SEM image of the cross section of n-PBDF fibers spun
at 2.50 total draw.

Information). The shape of the fibers changed from ribbon- WAXS characterization, the fibers were aligned in the meridional
shaped to bean-shaped with increasing draw (Figure S1, Support- direction; therefore, the appearance of equatorial arcs indicates
ing Information and Figure 1e) with their average circularity in- the preferred orientation of crystal planes parallel to the fiber axis
creasing from 0.53 to 0.83, and their average effective diameter direction. The total integrated intensity revealed two clear peaks
decreasing from 7.6 to 4.6 μm (Figure 1c, see Experimental Sec- (Figure 2c). The peak centered at 1.89 Å−1 (d-spacing of 3.33 Å) is
tion for more details on circularity and effective diameter calcu- attributed to the (010) 𝜋–𝜋 stacking of the n-PBDF chains, while
lation). The non-circular-shaped cross sections could stem from the peak centered at 0.58 Å−1 (d-spacing of 10.91 Å) is attributed
coagulation in the pure isopropanol bath leading to the forma- to the (100) lamella stacking between n-PBDF 𝜋–𝜋 stacks.[40] Ad-
tion of a dense coagulated skin in the outer perimeter of the fil- ditionally, the hump found at ≈1.15 Å−1 and the shoulder found
ament impeding further diffusion of solvents in and out of the at ≈1.75 Å−1 are attributed to the (200) and (300) reflections, re-
fiber. Upon drying, the uncoagulated center collapses leading to spectively. There are no striking differences between the total in-
a non-circular cross section.[25,43] This effect is mitigated at higher tensity patterns of the fibers spun at different draws. The inten-
draws due to the smaller diameters that lead to smaller diffusion sity of the (100) reflection increases with increasing draw with the
lengths and smaller volume to surface ratios. Figure 1d shows coherence lengths increasing from 5.8 nm at 1.05 draw to 6.9 nm
a scanning electron microscope (SEM) side-view of the n-PBDF at 2.50 draw (according to Lorentz fittings, Figure S2, Support-
fiber spun at 2.50 total draw with grooves and ridges observed on ing Information). The coherence length of the (010) reflection
the surface. This surface morphology is characteristic of fibers was found at 4.5 nm independent of the total draw. The intensity
that undergo a solvent diffusion-induced coagulation process, azimuthal profiles of the (100) and (010) reflections revealed dif-
and it is typically associated with the orientation of polymer fibrils ferences in the state of orientation of the fibers (Figure 2d,e). In
in the fiber axis direction.[43–45] these plots, peaks centered at 0° and 180° (equatorial direction)
2D wide angle X-ray scattering (WAXS) was used to study the indicate planes parallel to the fiber axis direction while peaks
structure and state of orientation of the different n-PBDF fiber centered at 90° (meridional direction) indicate planes perpendic-
samples. The 2D WAXS patterns of n-PBDF fibers spun at 1.05 ular to it. On one hand, the (100) reflection only shows peaks
and 2.50 total draws are shown in Figure 2a,b, respectively. In at 0° and 180°, indicating that the lamella stacking of n-PBDF
both cases, characteristic arcs centered along the equatorial line chains occurs parallel to the fiber axis direction as shown in the
are observed which are indicative of preferred orientation. For schematic structures in Figure 2f,g. Moreover, the peaks increase

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Figure 2. a,b) 2D WAXS patterns of n-PBDF fibers spun at total draws of a) 1.05 and b) 2.50. c) Total integrated intensity versus q value for each draw.
d,e) Azimuthal profiles for d) the (100) reflection and e) the (010) reflection. Peaks at 0° and 180° indicate parallel orientation with the fiber axis while a
peak at 90° indicates perpendicular orientation. f,g) Schemes of proposed structures with f) both (100) and (010) parallel to the fiber axis direction and
g) (100) parallel and (010) perpendicular to the fiber axis direction.

in intensity as the total draw is increased signaling an increase Figure 2e to increase in intensity as the draw increases indicat-
in preferred orientation. On the other hand, the (010) reflection ing a higher degree of orientation for both (010) and (001) planes.
azimuthal profile shows peaks at 0° and 180° and also at 90°. However, that is not what is observed since the peak at 90° de-
This hints at the existence of a bimodal orientation with some creases in intensity. Therefore, the observations seem to support
regions oriented with both the (100) and (010) planes parallel to the hypothesis that there exists a bimodal orientation in the n-
the fiber axis direction (Figure 2f) and other regions oriented with PBDF fibers.
the (100) planes parallel and the (010) planes perpendicular to the The n-PBDF fibers had high electrical conductivities that in-
fiber axis direction (Figure 2g). Bimodal orientation is not com- creased from ≈1000 S cm−1 to ≈1600 S cm−1 when the draw was
monly found in fibers since draw-induced crystallization typically increased from 1.05 to 2.50 (Figure 3a). These values of electrical
leads to unimodal orientation with the polymer chains oriented conductivity are among the highest reported in the literature for
in the fiber axis direction (as in Figure 2f). However, bimodal ori- n-type polymeric materials (Table S1, Supporting Information).
entation has been reported before for polypropylene fibers.[46] In The stress–strain curves (Figure 3b) are similar to those typical
polypropylene, flow-induced crystallization orients the lamellae of a polymer fiber with a yield point at around 1% strain. The
perpendicular to the flow direction, while drawing-induced crys- strain at break of the fibers decreased as the draw increased from
tallization does so parallel to the drawing direction.[47] A similar 16.8% to 8.4% while the break stress increased from 185 MPa
mechanism could be the origin of the bimodal orientation ob- to 248 MPa. Similarly, the Young’s modulus also increased from
served in the n-PBDF fibers. In that case, the (010) planes would 9.7 GPa at 1.05 draw to 19.5 GPa at 2.50 draw. This behavior is
orient perpendicular to the flow direction as they are extruded common in oriented polymer fibers. Interestingly, the electrical
through the capillary spinneret and then re-orient parallel to the conductivity increase correlates well with the increase in Young’s
fiber axis as they are drawn. Indeed, the intensity of the peaks at modulus (Figure 3c). This is because both electrical conductivity
0° and 180° increases with increasing draw, while the intensity and mechanical properties are affected similarly by inter- and in-
of the peak at 90° decreases (Figure 2e). It must be noted that trachain interactions. Indeed, charge carrier transport is fastest
there exists the possibility that the n-PBDF (001) d-spacing (at- along the conjugated polymer backbone while the backbone di-
tributed to the distance between repeating units) is similar to the rection is also the stiffest in tension.[18,48] In the framework of
𝜋–𝜋 stacking distance, and therefore the (010) and (001) reflec- the bimodal orientation present in the n-PBDF fibers, increas-
tions would have similar q values. In that case, the peak at 90° ing draw diminishes the proportion of the structure with the
(Figure 2e) would stem from the (001) reflection and it would polymer backbones aligned perpendicular to the fiber axis direc-
be oriented perpendicular to the fiber axis direction in the struc- tion (Figure 2g) in favor of the structure with the n-PBDF chains
ture shown in Figure 2f. Thus, a typical unimodal orientation for aligned parallel to it (Figure 2f); thus, improving both the elec-
fibers would be obtained. However, in that case, it would be ex- trical and mechanical properties of the fibers. Similarly, simul-
pected for both the peaks at 0° and 180° and the peak at 90° in taneous enhancement of electrical and mechanical properties by

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Figure 3. a) Electrical conductivity of the n-PBDF fibers versus the total draw applied during fabrication. Inset shows a digital camera picture of two
bundles of n-PBDF fibers hand-sewn into a cotton cloth that act as textile interconnections to light up an LED. Scale bar is 10 mm. b) Averaged tensile
stress-strain curves of the n-PBDF fibers. c) Electrical conductivity versus Young’s modulus showing the good correlation between these properties.
d) Stability study of the electrical conductivity of the fibers stored in different environments. The storage environments tested include 0.5–1% relative
humidity in air, 80% relative humidity in air and dry nitrogen. The total draw for these fibers was 1.50. e) OECT time-of-flight mobility for a 1.50 draw fiber.
Mobility values are average of 5 devices. f) Electrical conductivity (top), average Seebeck coefficient (mid) and thermoelectric power factor (bottom) of
the n-PBDF fibers over time up to 14 d since fabrication. In this case, the fibers were simply stored in the laboratory atmosphere without any special
relative humidity control.

drawing has been reported previously for poly(3-alkylthiophene) (Figure 3d). A spool was stored in a dry room in air with con-
fibers,[17,18] polyaniline fibers,[16] and PEDOT:PSS fibers.[25] The trolled relative humidity between 0.5-1%. The electrical conduc-
current density at break or ampacity of a n-PBDF fiber was mea- tivity of this sample decreased to ≈56% of its initial conductivity
sured at 7.25 kA cm−2 which is close to ampacity values for PE- after 14 d. A second spool was stored in an environmental cham-
DOT:PSS fibers[26] (Figure S3, Supporting Information). The n- ber in air at room temperature and 80% relative humidity. The
PBDF fibers are resilient enough to withstand manipulation, in electrical conductivity of this sample decreased to ≈81% of its
fact, bundles of tens of n-PBDF fibers were threaded through the initial conductivity after 14 d. Lastly, a third spool was stored in
head of a sewing needle and hand-sewn to a cotton cloth to make dry nitrogen within a laboratory glovebox. The electrical conduc-
contacts to light up an LED (see inset of Figure 3a). tivity of this sample decreased to ≈83% of its initial conductivity
One of the biggest limitations of n-type polymer materials is after 14 d. In addition to this, we also monitored the stability of
their environmental stability; therefore, we closely studied the the charge carrier mobility in the fibers over time, by measur-
stability of the n-PBDF fibers. n-PBDF thin films have been previ- ing the time-of-flight mobility in organic electrochemical tran-
ously reported to have good environmental stability.[41] However, sistors (OECT) fabricated using a n-PBDF fiber (stored in lab-
we observed a decrease in the electrical conductivity of the fibers oratory atmosphere) as the channel (Figure 3e, see Experimen-
over the first few days since fabrication when stored in labora- tal Section and Figure S4, Supporting Information for details on
tory atmosphere (see top panel of Figure 3f). It must be noted OECT fabrication and mobility calculation).[49] The time-of-flight
that after the initial days, the electrical conductivity seemed to be mobility was measured at 5.7 cm2 V−1 s−1 on day 0 and decreased
tending towards an equilibrium value and even after 14 days of by 25% to 4.2 cm2 V−1 s−1 on day 14. It is worth noting that
degradation, the electrical conductivity remained in the range of these time-of-flight mobility values are higher than previously
400 to 800 S cm−1 depending on the applied draw, which is still a reported from the transfer characteristics in n-type OECTs,[29,50]
relatively high conductivity for an n-type material (see Table S1, which may further highlight that the exceptional alignment of
Supporting Information). To better understand the degradation the polymer chains in the fibers leads to faster charge transport.
mechanism, we stored spools of n-PBDF fibers in different en- Similar exceptionally high time-of-flight mobility values (as high
vironments and monitored their electrical conductivity over time as 45 cm2 V−1 s−1 ) have also been reported for highly aligned

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PEDOT:PSS fiber-based OECT.[51] The slight decrease in mobility coagulated or phase-inverted in isopropanol to rapidly form the
could explain the decrease in electrical conductivity that occurred solid n-PBDF fibers. On the other hand, the n-PBDF films were
even when the fibers were stored in dry nitrogen atmosphere but formed by comparatively slow evaporation of the n-PBDF solvent,
does not account for the 50% decrease that occurred in dry air. We DMSO.[41]
must note that the reason for the decrease in mobility of the fibers A common parameter to compare the thermoelectric perfor-
stored under nitrogen atmosphere is currently unknown and still mance between polymer materials is the thermoelectric power
under investigation. From these results, oxygen exposure seems factor, PF, which is the product of the electrical conductivity and
to be the main culprit of the electrical conductivity degradation. the Seebeck coefficient squared, PF = S2 𝜎. A good thermoelec-
Interestingly, the n-PBDF fibers were more stable when stored in tric material thus would have both a high electrical conductiv-
high relative humidity than in dry conditions. This observation ity and a high Seebeck coefficient. However, in practice, this is
is consistent with n-PBDF undergoing n-type doping via water challenging to achieve because while the electrical conductivity
oxidation with H+ acting as counterions in the reduced PBDF is directly proportional to the charge carrier concentration, the
structure.[40,41] The proposed dedoping mechanism upon expo- Seebeck coefficient is inversely related.[52] Typically, a compro-
sure to air involves oxygen reduction consuming both the H+ mise of these properties is sought such that the power factor
counterions and electrons, oxidizing n-PBDF to the neutral state, is maximized. For example, it is common to chemically dedope
and producing water (Equation 1). This oxidation of n-PBDF is PEDOT:PSS to slightly reduce its conductivity while increasing
only favorable in the heavily doped form, where the work func- its Seebeck coefficient.[54] Interestingly, in these n-PBDF fibers,
tion of n-PBDF is approximately 4.6 eV and there are electrons at some amount of dedoping apparently occurs via reaction with
the Fermi energy.[41] In the neutral form, and likely the lightly n- oxygen in the air (Equation 1), and the drop in conductivity over
doped form, the HOMO and LUMO energies are such that this time is compensated by the enhancement of the Seebeck coeffi-
oxidation reaction will not occur.[41] Additionally, if the concen- cient, leading to an increase of the thermoelectric power factor of
tration of water in the environment is high (for instance, high the fibers over time (bottom panel of Figure 3f). Indeed, the high-
relative humidity air) the equilibrium is displaced towards the est power factor was calculated at 91 μW m−1 K−2 for the n-PBDF
reactants and fewer, if any, n-PBDF chains are oxidized to their fibers processed at 2.50 total draw after 14 d, which is a remark-
neutral state. able value for an n-type polymeric material (Table S1, Supporting
Information).
O2 + 4 PBDF− + 4 H+ ⇌ 2 H2 O + 4 PBDF0 (1) As proof of concept, we fabricated a thermoelectric textile de-
vice using n-type PBDF fibers and complementary p-type PE-
The Seebeck coefficient of the n-PBDF fibers was found to DOT:PSS fibers (Figure 4a). Since the thermoelectric perfor-
be unaffected by draw with an average value of −19 μV K−1 mance of the n-PBDF fibers improved over time and seemed to
measured on the same day of fabrication. Moreover, the See- reach stable values after two weeks (see Figure 3f), 15 day old
beck coefficient increased in absolute value over time, reach- n-type PBDF fibers were used in the device fabrication. The PE-
ing an average value of −33 μV K−1 after 14 d of the fibers be- DOT:PSS fibers were fabricated following a process previously
ing stored in laboratory atmosphere (mid panel of Figure 3f). reported by our group and their electrical conductivity was ≈2000
The Seebeck coefficient depends strongly on the charge carrier S cm−1 with a Seebeck coefficient of ≈15 μV K−1 .[25] To fabricate
concentration of the polymer and, in general, decreases with the thermoelectric device, bundles of tens of n-PBDF and PE-
increasing charge carrier concentration.[29,52] Thus, increasing DOT:PSS fibers were hand-sewn in an alternate fashion yielding
draw resulted in a higher degree of polymer chain alignment a two-couple device (see scheme in Figure 4b) with an internal
in the fiber axis direction, enhancing charge carrier transport resistance of 513 Ω. The electrical connections between n-PBDF
but did not increase the charge carrier concentration (i.e., draw- and PEDOT:PSS fiber bundles were made by placing a small drop
ing did not induce further doping of the n-PBDF chains). Simi- of silver paint at the contact points. As expected, the open circuit
lar results have been reported for PEDOT:PSS[25] and poly(2,5- voltage generated increased linearly by increasing the tempera-
dimethoxyphenylenevinylene).[53] However, the increase in the ture gradient across the textile device (Figure 4c). The two-couple
absolute value of the Seebeck coefficient over time suggests that device had a device Seebeck coefficient of 101.5 μV K−1 , equiv-
the charge carrier concentration decreased with time (n-PBDF alent to ≈50.7 μV K−1 per couple. The Seebeck coefficient of a
chains oxidized to their neutral state), which supports the hy- single thermoelectric couple is equal to the sum of the absolute
pothesis of the degradation via oxygen reduction as proposed in value of the Seebeck coefficients of its constituent n-type and p-
Equation 1. In summary, on one hand, drawing the fibers im- type materials. In this case, the value is in good agreement with
proved their charge carrier mobility which increased the electri- the sum of roughly −35 μV K−1 and 15 μV K−1 for 15 day old
cal conductivity but had no effect on the Seebeck coefficient. On n-PBDF fibers and PEDOT:PSS fibers, respectively. The output
the other hand, the degradation of the fibers over time reduced power generated by the device was evaluated at a temperature
the charge carrier concentration which, in turn, decreased the gradient of 22 °C by connecting a series of loads to the device and
electrical conductivity but increased the Seebeck coefficient. We measuring the output current and voltage (Figure 4d). The two-
note here, that the drop in electrical conductivity over time ob- couple device generated a maximum output power of 2.40 nW
served in n-PBDF fibers contrasts with the stable electrical con- at the load that most closely matched the internal resistance of
ductivity observed in thin films.[41] This is an area under inves- the device. The experimental values obtained were in good agree-
tigation but we hypothesize the difference might stem from the ment with the predicted values derived from the equivalent cir-
two very distinct processing methods utilized to fabricate the two cuit using the measured device internal resistance (513 Ω) and
different materials geometries. Indeed, the n-PBDF solution was couple Seebeck coefficient (50.7 μV K−1 ).

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Figure 4. a) Photograph of the two-couple thermoelectric textile fabricated by hand-sewing bundles of n-type PBDF fibers and p-type of PEDOT:PSS
fibers to a cotton cloth. b) Scheme of the thermoelectric textile. c) Generated open circuit voltage versus the temperature gradient across the device.
The slope of the linear fit represents the device Seebeck coefficient. d) Output power curves of the thermoelectric device at a temperature gradient of
22 °C. Each data point corresponds to a different load connected to the device. The dashed lines are the predicted values calculated from an equivalent
circuit using the measured internal resistance and device Seebeck coefficient.

3. Conclusions air but it was found to be significantly more stable if the fibers
were stored in dry nitrogen or high humidity air. This suggested
There is a gap in the field of electronic textiles with regard to elec- that the degradation occurred via oxygen oxidizing the n-PBDF
trically conductive fibers with n-type characteristics. The current chains. This observation was supported by the Seebeck coeffi-
lack of n-type polymer fibers stems from the challenges in devel- cient of the fibers increasing in absolute value over time. Despite
oping stable and highly conductive n-type polymers compared to the drop in conductivity over time, the increase in the Seebeck co-
their more established p-type counterparts. However, recent sci- efficient resulted in the highest thermoelectric power factor be-
entific breakthroughs have closed that gap significantly. In this ing measured at 91 μW m−1 K−2 for the most drawn fibers, 14
work, we built upon those breakthroughs to wet-spin for the first- d after fabrication. As a demonstration, the n-type PBDF fibers
time n-type polymer fibers from pure n-PBDF. The fibers dis- were used to complement p-type PEDOT:PSS fibers in the fab-
played high electrical conductivities in the range from 1000 to rication of a hand-sewn two-couple textile thermoelectric device
1600 S cm−1 depending on the total draw applied during pro- that could generate 2.40 nW at a temperature gradient of 22 °C.
cessing. The structure and orientation of the fibers were stud- These results represent the initial steps towards the fabrication of
ied using WAXS and a bimodal orientation of the crystal planes pure n-type polymer fibers that match and complement the more
was observed. One orientation mode corresponded to the (100) established p-type polymer fibers.
and (010) planes and, therefore, the n-PBDF backbones, oriented
parallel to the fiber axis direction. While the other orientation
mode had the (100) planes parallel and the (010) planes perpen-
dicular to the fiber axis direction, in which case the polymer 4. Experimental Section
backbones were also oriented perpendicular. Increasing the to- Materials: n-PBDF:DMSO solution was synthesized as in previous
tal draw, changed the preferred state of orientation towards the research.[41] Isopropanol was purchased from VWR. Silver paint to make
former orientation mode, such that more n-PBDF backbones contacts to the fibers was purchased from Electron Microscope Sciences.
oriented parallel to the fiber axis direction. The simultaneous Wet-Spinning Process: The n-PBDF:DMSO solution was used as re-
enhancement of electrical and mechanical properties with in- ceived. The solution was loaded into a 5 mL plastic syringe and placed
creased applied draw was attributed to this increase in poly- on a syringe pump (KD Scientific). The flow rate was precisely controlled
and maintained constant at 0.25 mL h−1 . A 5 μm nylon 6-6 syringe filter
mer chain alignment. The electrical conductivity of the fibers de- was used to filter out any impurities. The n-PBDF solution was extruded
creased over time when stored in laboratory atmosphere or dry through a 100 μm capillary spinneret with a 500 μm of capillary length.

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Isopropanol was used as coagulation bath at room temperature. The co- using Scherrer’s equation with a dimensionless shape factor of 1 for fiber
agulated fibers were continuously collected from the bath using a rotating materials.[55,56]
roller. The distance between the rotating roller and the coagulation bath Organic Electrochemical Transistor Fabrication and Characterization:
was about 15 cm and enough for the thin fibers to air dry before reaching The n-type PBDF fibers were used as the active channel material to fab-
the roller. The total draw is the ratio between the linear speed of the rotat- ricate OECT devices. Five OECT devices were fabricated fresh and charac-
ing roller and the jet velocity (flow rate divided by the area of the spinneret terized at 0, 7, and 14 d since the fabrication of the fibers. The fibers utilized
orifice). Fibers were collected at draw ratios of 1.05, 1.50, 2.00 and 2.50 by for this purpose were stored in laboratory atmosphere. The OECT fabrica-
varying the rotating roller speed while keeping the flow rate constant. tion process involved placing two graphite foils on a 3D-printed support
Scanning Electron Microscopy: A Hitachi S-4800 field emission SEM at structure serving as source and drain electrodes, followed by positioning
10 kV accelerating voltage and 10 μA beam current was utilized for imag- an n-PBDF fiber on top of the electrodes. Graphite paint (Graphite Con-
ing. The conductive fibers were imaged without the need for sputtering ductive Adhesive 154, Electron Microscopy Sciences) was then applied to
gold. To get accurate values of cross-sectional area, bundles of fibers were establish electrical contact between the fiber and the electrodes. The fiber
fractured while immersed in liquid nitrogen using a new razor blade. Val- was suspended above a well that was then filled with the electrolyte solu-
ues of cross-sectional area, A, and perimeter, P, were obtained for several tion (aqueous 0.1 m NaCl) in which the gate (Ag/AgCl) was submerged.
fibers per sample. The effective diameter was calculated as the diameter The contacts were not wetted by the electrolyte, and it was ensured nearly
that would yield an equivalent circular area. The circularity was calculated full coverage of the fiber by the electrolyte solution. The device length was
as follows: measured with a caliper and found to be approximately 1 cm. The devices
were placed on a microscope station, and, with two microprobes, con-
4𝜋A tact was made to the source and drain electrodes. A Keysight B2912A
Circularity = (2)
P2 Precision Source/Measure Unit was employed to measure the current-
voltage characteristics. To determine mobility values, the transient or time-
The error bars in effective diameter and circularity represent the stan- of-flight method outlined by Bernard and Malliaras[49] was followed. The
dard deviation. method involved applying varying gate current pulses, IG , at a constant
Mechanical Characterization: An automatic single-fiber test system, drain voltage, VD , of 0.15 V while measuring the source–drain current, ID ,
FAVIMAT+ from Textechno was used to perform tensile tests on the fibers. response as displayed in Figure S4a (Supporting Information). The slope
The pretension was 0.50 cN per tex and the test speed was 5.0 mm min−1 of the source–drain current versus time, dID /dt, was calculated and plotted
over a gauge length of 25.4 mm. Additionally, the FAVIMAT+ system was against the gate current for each case (Figure S4b, Supporting Informa-
also used to measure the average linear density of each tested specimen tion). The inverse of the electronic transient time, 𝜏, was obtained from
using an ultrasonic resonance method. The values presented in this work the slope of this plot. The device mobility, 𝜇, was then calculated using
are average values of at least 5 fiber specimens and error bars represent Equation 4.
standard deviation.
Electrical and Thermoelectrical Characterization: Fibers were laid be- 𝜏 = L2 ∕𝜇VD (4)
tween two copper tape strips and contacted using silver paint. For each
sample, the resistance of fibers of different lengths (typically 20, 30, 40 Fabrication and Characterization of the Thermoelectric Textile: Bundles
and 50 mm) were measured in 2-probe configuration using a Keithley 2401 composed of tens of parallel 15 d old n-PBDF fibers and PEDOT:PSS fibers
source-meter. A resistance versus length plot was constructed and the con- were threaded through the head of a sewing needle and hand-sewn to an
tact resistance was extracted from the y-axis intercept (see Figure S5, Sup- embroidery cotton cloth in an alternating fashion. The n-PBDF fiber bun-
porting Information for an example plot). The electrical conductivity, 𝜎, dles and PEDOT:PSS fiber bundles were joined together by placing a small
was calculated using the resistance per length, R/L, and cross-sectional drop of silver paint between them. Similarly, silver paint was used at the ex-
area, A, of the fibers. tremes of the device to interface with the probes of a Keithley 2100 digital
multimeter that was used to measure the open circuit voltage as a func-
L tion of temperature gradient and the output current for different applied
𝜎 = (3)
RA loads. To achieve a temperature gradient, one side of the thermoelectric
textile was attached to a Peltier plate which allowed precise control of the
At least four specimens were tested per sample and the values reported temperature. The other side was left at room temperature. Two K-type ther-
are average values while error bars represent the standard deviation be- mocouples were used to monitor the hot-side and cold-side temperatures.
tween specimens.
The Seebeck coefficient was measured using an in-house built setup.
Typically, three 30 mm long fiber segments were laid such that one of their Supporting Information
ends was on top of a Peltier device. The Peltier device was used to pre-
Supporting Information is available from the Wiley Online Library or from
cisely control the temperature of that side while the other side was simply
the author.
kept at room temperature. Two K-type thermocouples were used to mon-
itor the cold-side and hot-side temperatures. The thermoelectric voltage
generated was monitored using a Keithley 2100 multimeter. The Seebeck
coefficient was extracted as the slope of the ΔV–ΔT plots. The Seebeck co-
Acknowledgements
efficient values presented are an average of at least three fiber specimens The authors gratefully acknowledge Augustine O. Yusuf for additional con-
and the error represent the standard deviation. ductivity and Seebeck coefficient testing. Z.K. and J.M. gratefully acknowl-
Wide-Angle X-Ray Scattering: A Xenocs Xeuss 2.0 SAXS/WAXS system edge support from the Office of Naval Research (N00014-22-1-2177, Pro-
located at the Electron Microscopy Center of the University of Kentucky gram Manager: Dr. Paul Armistead). This material is based upon work sup-
was used to perform WAXS measurements in transmission mode. The ported by the National Science Foundation under Cooperative Agreement
source was GeniX3D Cu ULD 8 keV with a wavelength of 1.54189 Å. Typi- No. 1849213. Any opinions, findings, and conclusions or recommenda-
cally, a bundle containing tens of fibers was aligned in an aperture card. tions expressed in this material are those of the authors and do not nec-
The aperture card was then transferred to the WAXS sample holder and essarily reflect the views of the National Science Foundation.
placed at 105.9 mm from the 2D detector (Dectris Pilatus 200 K). Expo-
sure time was 1200 s. Data processing to obtain the integrated intensity
and azimuthal angle profiles was performed using the software Foxtrot Conflict of Interest
provided by Xenocs. Data analysis and peak fitting were done using Orig-
inPro software. The coherence length was calculated from Lorentz fittings The authors declare no conflict of interest.

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