6 research outputs found
Polarity and Air-Stability Transitions in Field-Effect Transistors Based on Fullerenes with Different Solubilizing Groups
A series of <i>o</i>-xylene
and indene fullerene derivatives with varying frontier molecular orbital
energy levels were utilized for assessing the impact of the number
of solubilizing groups on the electrical performance of fullerene-based
organic-field-effect transistors (OFETs). The charge-carrier polarity
was found to be strongly dependent upon the energy levels of fullerene
derivatives. The <i>o</i>-xylene C<sub>60</sub> monoadduct
(OXCMA) and indene C<sub>60</sub> monoadduct (ICMA) exhibited unipolar <i>n</i>-channel behaviors with high electron mobilities, whereas
the bis- and trisadducts of indene and <i>o</i>-xylene C<sub>60</sub> derivatives showed ambipolar charge transport. The OXCMA
OFETs fabricated by solution shearing and molecular <i>n</i>-type doping showed an electron mobility of up to 2.28 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup>, which is one of the
highest electron mobilities obtained from solution-processed fullerene
thin-film devices. Our findings systematically demonstrate the relationship
between the energy level and charge-carrier polarity and provide insight
into molecular design and processing strategies toward high-performance
fullerene-based OFETs
Controlling Number of Indene Solubilizing Groups in Multiadduct Fullerenes for Tuning Optoelectronic Properties and Open-Circuit Voltage in Organic Solar Cells
The ability to tune the lowest unoccupied molecular orbital
(LUMO)/highest
occupied molecular orbital (HOMO) levels of fullerene derivatives
used as electron acceptors is crucial in controlling the optical/electrochemical
properties of these materials and the open circuit voltage (<i>V</i><sub>oc</sub>) of solar cells. Here, we report a series
of indene fullerene multiadducts (ICMA, ICBA, and ICTA) in which different
numbers of indene solubilizing groups are attached to the fullerene
molecule. The addition of indene units to fullerene raised its LUMO
and HOMO levels, resulting in higher <i>V</i><sub>oc</sub> values in the photovoltaic device. Bulk-heterojunction (BHJ) solar
cells fabricated from polyÂ(3-hexylthiophene) (P3HT) and a series of
fullerene multiadducts-ICMA, ICBA, and ICTA showed <i>V</i><sub>oc</sub> values of 0.65, 0.83, and 0.92 V, respectively. Despite
demonstrating the highest <i>V</i><sub>oc</sub> value, the
P3HT:ICTA device exhibited lower efficiency (1.56%) than the P3HT:ICBA
device (5.26%) because of its lower fill factor and current. This
result could be explained by the lower light absorption and electron
mobility of the P3HT:ICTA device, suggesting that there is an optimal
number of the solubilizing group that can be added to the fullerene
molecule. The effects of the addition of solubilizing groups on the
optoelectrical properties of fullerene derivatives were carefully
investigated to elucidate the molecular structure–device function
relationship
Importance of Optimal Composition in Random Terpolymer-Based Polymer Solar Cells
A new series of donor–acceptor
(D–A) conjugated random
terpolymers (PBDTT–DPP–TPD) were synthesized from electron-rich
thienyl-substituted benzoÂ[1,2-<i>b</i>:4,5-<i>b</i>′]Âdithiophene (BDTT), in conjugation with two electron-deficient
units, pyrroloÂ[3,4-<i>c</i>]Âpyrrole-1,4-dione (DPP) and
thienoÂ[3,4-<i>c</i>]Âpyrrole-4,6-dione (TPD), of different
electron-withdrawing strengths. The optical properties of these random
terpolymers can be easily controlled by tuning the ratio between DPP
and TPD; an increase in TPD induced increased absorption between 400
and 650 nm and a lower highest occupied molecular orbital energy level,
while higher DPP contents resulted in stronger absorption between
600 and 900 nm. The best power conversion efficiency (PCE) of 6.33%
was obtained from PBDTT–DPP75–TPD25 with [6,6]-phenyl-C<sub>71</sub>-butyric acid methyl ester (PC<sub>71</sub>BM) due to the
improved light absorption and thus a short-circuit current density
(<i>J</i><sub>SC</sub>) higher than 16 mA/cm<sup>2</sup>. Interestingly, the trend observed in the PCE values differed from
that of optical behavior of the PBDTT–DPP–TPD in terms
of the DPP to TPD ratio, showing nonlinear compositional dependence
from 2 to 6%. Density functional theory calculations showed that the
small portions of strong electron-withdrawing DPP in PBDTT–DPP25–TPD75
and PBDTT–DPP10–TPD90 could provide trap sites, which
suppress efficient charge transfer. In contrast, for PBDTT–DPP90–TPD10
and PBDTT–DPP75–TPD25, the effect of minor portions
of TPD on electron density distribution was found to be minimal. In
addition, the polymer packing and nanomorphology were investigated
by grazing-incidence X-ray scattering and atomic force microscopy.
The findings suggested that controlling the ratio of electron-deficient
units in the random terpolymers is critical for optimizing their performance
in polymer solar cells because it affects the polymer packing structure,
the optical and electrical properties, and the electron distribution
in the polymers
Effect of Incorporated Nitrogens on the Planarity and Photovoltaic Performance of Donor–Acceptor Copolymers
Systematic control of the chemical structure of conjugated
polymers is critically important to elucidate the relationship between
the conjugated polymer structures and properties and to optimize their
performance in bulk heterojunction (BHJ) polymer solar cell (PSC)
devices. Herein, we synthesized three new copolymers, i.e., <b>P0</b>, <b>P1</b>, and <b>P2</b>; these copolymers
contain the same benzodithiophene donor unit but have different acceptor
units with different numbers of nitrogen atoms in the range of 0–2.
The effects of the introduced nitrogen atoms on the structural, optical,
electrical, and photovoltaic properties of the conjugated polymers
were investigated; the structural properties of the polymers, in particular,
were studied using both experimental (grazing-incidence X-ray scattering
(GIXS) measurements) and computational methods (molecular simulation).
As the number of introduced nitrogen atoms increased, the planarity
of the main chain conformation increased in the order of <b>P0</b> < <b>P1</b> < <b>P2</b>. Additionally, the <b>P0</b>, <b>P1</b>, and <b>P2</b> polymers showed increased
interlayer domain spacings of 1.61, 1.72, and 1.78 nm, respectively,
with increased intermolecular ordering. These results were in excellent
agreement with the simulation results. In addition, the enhanced planarity
resulted in a red-shifting at the onset of absorption in the polymer
film from 544 to 585 nm, a downshift in the lowest unoccupied molecular
orbital (LUMO) energy level from −3.02 to −3.26 eV,
and an increase in the hole mobility from 2.33 × 10<sup>–6</sup> to 3.78 × 10<sup>–5</sup> cm<sup>2</sup>/(V s). As a
result, we observed dramatically enhanced performance of the PSCs
in the order of <b>P0</b> < <b>P1</b> < <b>P2</b>. For example, the <b>P2</b>:PC<sub>61</sub>BM device exhibited
a 3.5-fold improvement in power conversion efficiency (PCE) compared
to that of <b>P0</b>:PC<sub>61</sub>BM. The further optimization
of <b>P2</b> with PC<sub>71</sub>BM showed the PCE of 3.22%
Photoinduced Charge Transfer in Donor–Acceptor (DA) Copolymer: Fullerene Bis-adduct Polymer Solar Cells
Polymer solar cells (PSCs) consisting of fullerene bis-adduct
and polyÂ(3-hexylthiophene) (P3HT) blends have shown higher efficiencies
than P3HT:phenyl C<sub>61</sub>-butyric acid methyl
ester (PCBM) devices, because of the high-lying lowest unoccupied
molecular orbital (LUMO) level of the fullerene bis-adducts. In contrast,
the use of fullerene bis-adducts in donor–acceptor (DA) copolymer
systems typically causes a decrease in the device’s performance
due to the decreased short-circuit current (<i>J</i><sub>SC</sub>) and the fill factor (FF). However, the reason for such
poor performance in DA copolymer:fullerene bis-adduct blends is not
fully understood. In this work, bulk-heterojunction (BHJ)-type PSCs
composed of three different electron donors with four different electron
acceptors were chosen and compared. The three electron donors were
(1) polyÂ[(4,8-bis-(2-ethylhexyloxy)ÂbenzoÂ[1,2-<i>b</i>:4,5-<i>b</i>′]Âdithiophene)-2,6-diyl-<i>alt</i>-(5-octylthienoÂ[3,4-<i>c</i>]Âpyrrole-4,6-dione)-1,3-diyl] (PBDTTPD), (2) polyÂ[(4,8-bis-(2-ethylhexyloxy)benzoÂ[1,2-<i>b</i>:4,5-<i>b</i>′]Âdithiophene)-2,6-diyl-<i>alt</i>-(4-(2-ethylhexanoyl)-thienoÂ[3,4-<i>b</i>]Âthiophene)-2,6-diyl] (PBDTTT-C), and (3) P3HT polymers.
The four electron acceptors were (1) PCBM, (2) indene-C<sub>60</sub> monoadduct (ICMA), (3) indene-C<sub>60</sub> bis-adduct (ICBA),
and (4) indene-C<sub>60</sub> tris-adduct (ICTA). To understand the
difference in the performance of BHJ-type PSCs for the three different
polymers in terms of the choice of fullerene acceptor, the structural,
optical, and electrical properties of the blends were measured by
the external quantum efficiency (EQE), photoluminescence, grazing
incidence X-ray scattering, and transient absorption spectroscopy.
We observed that while the molecular packing and optical properties
cannot be the main reasons for the dramatic decrease in the PCE of the DA copolymers and ICBA, the value of the driving force for
charge transfer (Δ<i><i>G</i></i><sub>CT</sub>) is a key parameter for determining the change in <i>J</i><sub>SC</sub> and device efficiency in the DA copolymer- and P3HT-based PSCs in
terms of fullerene acceptor. The low EQE and <i>J</i><sub>SC</sub> in PBDTTPD and PBDTTT-C blended with ICBA and ICTA were
attributed to an insufficient <i>Δ<i>G</i></i><sub>CT</sub> due to the higher LUMO levels of the fullerene multiadducts.
Quantitative information on the efficiency of the charge transfer
was obtained by comparing the polaron yield, lifetime, and exciton
dissociation probability in the DA copolymer:fullerene acceptor films
Highly Luminescent Polymer Particles Driven by Thermally Reduced Graphene Quantum Dot Surfactants
We report the use of highly luminescent
graphene quantum dots (GQDs)
as efficient surfactants to produce Pickering emulsions and novel
polymer particles. To generate the GQD surfactants, the surface properties
of 10 nm sized, non-reduced GQDs (nGQDs), which have strong hydrophilicity,
were synthesized and modified in a systematic manner by the thermal
reduction of oxygen-containing groups at different treatment times.
In stark contrast to the behavior of the nGQDs, thermally reduced
GQDs (rGQDs) can produce highly stable Pickering emulsions of oil-in-water
systems. To demonstrate the versatility of the rGQD surfactants, they
were applied in a mini-emulsion polymerization system that requires
nanosized surfactants to synthesize submicron-sized polystyrene particles.
In addition, the use of rGQD surfactants can be extended to generating
block copolymer particles with controlled nanostructures. Particularly,
the polymer particles were highly luminescent, a characteristic produced
by the highly fluorescent GQD surfactants, which has great potential
for various applications, including bioimaging, drug delivery, and
optoelectronic devices. To the best of our knowledge, this is the
first report in which nanosized GQDs were used as surfactants