Advanced Materials,
Год журнала:
2022,
Номер
35(8)
Опубликована: Дек. 9, 2022
The
development
of
unipolar
n-type
semiconducting
polymers
with
electron
mobility
(µe
)
over
5
cm2
V-1
s-1
remains
a
massive
challenge
in
organic
semiconductors.
Diketopyrrolopyrrole
(DPP)
has
proven
to
be
successful
unit
for
high-performance
p-type
and
ambipolar
polymers.
However,
DPP's
moderate
electron-accepting
capability
leads
the
shallow
frontier
molecular
orbital
(FMO)
levels
resultant
hence
limit
µe
transistors.
Herein,
this
issue
been
addressed
by
using
hybrid
acceptor-modulation
strategy
based
on
DPP-containing
"fluorinated
triple-acceptor
architecture",
namely
DPP-difluorobenzothiadiazole-DPP
(DFB).
Compared
DFB's
non-fluorinated
counterpart,
DFB
features
deeper
FMO
shape-persistent
framework.
Therefore,
series
DFB-based
demonstrate
planar
backbones
lowered
≈0.10
0.25
eV
versus
that
control
polymer.
Intriguingly,
all
DFB-polymers
exhibit
excellent
transistor
performances.
Notably,
full-locked
backbone
conformation
high
crystallinity
crystalline
coherence
length
524
Å
are
observed
pDFB-TF,
accounting
its
5.04
,
which
is
highest
value
DPP-based
reported
date.
This
work
demonstrates
architecture"
opens
new
path
towards
Advanced Materials,
Год журнала:
2024,
Номер
36(25)
Опубликована: Март 21, 2024
Abstract
Currently,
high‐performance
polymerized
small‐molecule
acceptors
(PSMAs)
based
on
ADA‐type
SMAs
are
still
rare
and
greatly
demanded
for
polymer
solar
cells
(PSCs).
Herein,
two
novel
regioregular
PSMAs
(PW‐Se
PS‐Se)
designed
synthesized
by
using
centrosymmetric
(linear‐shaped)
axisymmetric
(banana‐shaped)
as
the
main
building
blocks,
respectively.
It
is
demonstrated
that
photovoltaic
performance
of
can
be
significantly
improved
optimizing
configuration
SMAs.
Compared
to
SMA‐based
(PS‐Se),
PW‐Se
a
SMA
block
exhibits
better
backbone
coplanarity
thereby
resulting
in
bathochromically
shifted
absorption
with
higher
coefficient,
tighter
interchain
π–π
stacking,
more
favorable
blend
film
morphology.
As
result,
enhanced
more‐balanced
charge
transport,
exciton
dissociation,
reduced
recombination
achieved
PW‐Se‐based
devices
PM6
donor.
Benefiting
from
these
positive
factors,
optimal
PM6:PW‐Se‐based
device
power
conversion
efficiency
(PCE)
15.65%
compared
PM6:PS‐Se‐based
(8.90%).
Furthermore,
incorporation
third
component
binary
active
layer
PM6:M36
yields
ternary
an
outstanding
PCE
18.0%,
which
highest
value
PSCs
SMAs,
best
knowledge.
Fine-tuning
the
charge
polarity
and
enhancing
electron
transport
in
conjugated
polymers
are
critical
for
developing
high-performance
organic
field-effect
transistors
(OFETs).
Quinoidal
polymers,
characterized
by
planar
backbones
deep-lying
lowest
unoccupied
molecular
orbital
(LUMO)
energy
levels,
offer
distinct
advantages
over
their
aromatic
counterparts
but
face
challenges
achieving
reliable
mobilities
exceeding
1
cm2
V–1
s–1.
Herein,
we
synthesized
a
set
of
novel
quinoid–donor–acceptor
(Q-D-A)
with
various
acceptor
units.
Increasing
strength
narrowed
band
gap,
lowered
LUMO
shifted
from
unipolar
p-type
to
ambipolar
ultimately
dominant
n-type
behavior.
The
electron-to-hole
mobility
ratio
increased
0
40
behavior
observed
Q-D-A
polymer
first
time.
Consequently,
strongest
acceptor-based
exhibited
backbone,
small
effective
mass,
high
crystallinity,
low
disorder,
resulting
1.20
s–1
decent
operational
stability.
This
is
record-high
value
quinoidal
transport.
Our
findings
viable
strategy
tuning
improving
providing
insights
into
structure–property
relationships
essential
advancing
electronics.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
describes
the
design
considerations,
bonding
modes
between
monomers,
structural
modification
strategies,
and
applications
of
polymer
semiconductors
with
excellent
electron
transport
performances.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(32)
Опубликована: Июнь 8, 2022
Abstract
The
development
of
high‐performance
n‐type
polymer
semiconductors
is
powered
by
the
design
and
synthesis
electron‐deficient
building
blocks
with
optimized
physicochemical
properties.
By
meticulously
installing
an
imide
group
onto
fluorene
its
cyanated
derivative,
we
report
here
two
very
blocks,
imide‐functionalized
fluorenone
(
FOI
)
derivative
FCNI
),
both
featuring
a
deep‐lying
lowest
unoccupied
molecular
orbital
energy
level
down
to
−4.05
eV
highly
coplanar
framework,
endowing
them
ideal
units
for
constructing
polymers.
Thus,
series
polymers
are
built
from
them,
exhibiting
unipolar
transport
character
highest
electron
mobility
0.11
cm
2
V
−1
s
.
Hence,
offer
remarkable
platform
accessing
functionalization
appropriate
(hetero)arenes
powerful
strategy
developing
LUMOs
organic
electronics.
Advanced Materials,
Год журнала:
2022,
Номер
35(8)
Опубликована: Дек. 9, 2022
The
development
of
unipolar
n-type
semiconducting
polymers
with
electron
mobility
(µe
)
over
5
cm2
V-1
s-1
remains
a
massive
challenge
in
organic
semiconductors.
Diketopyrrolopyrrole
(DPP)
has
proven
to
be
successful
unit
for
high-performance
p-type
and
ambipolar
polymers.
However,
DPP's
moderate
electron-accepting
capability
leads
the
shallow
frontier
molecular
orbital
(FMO)
levels
resultant
hence
limit
µe
transistors.
Herein,
this
issue
been
addressed
by
using
hybrid
acceptor-modulation
strategy
based
on
DPP-containing
"fluorinated
triple-acceptor
architecture",
namely
DPP-difluorobenzothiadiazole-DPP
(DFB).
Compared
DFB's
non-fluorinated
counterpart,
DFB
features
deeper
FMO
shape-persistent
framework.
Therefore,
series
DFB-based
demonstrate
planar
backbones
lowered
≈0.10
0.25
eV
versus
that
control
polymer.
Intriguingly,
all
DFB-polymers
exhibit
excellent
transistor
performances.
Notably,
full-locked
backbone
conformation
high
crystallinity
crystalline
coherence
length
524
Å
are
observed
pDFB-TF,
accounting
its
5.04
,
which
is
highest
value
DPP-based
reported
date.
This
work
demonstrates
architecture"
opens
new
path
towards
