Abstract
There
is
a
noticeable
gap
in
the
literature
regarding
research
on
halogen‐substitution‐regulated
ferroelectric
semiconductors
featuring
multiple
phase
transitions.
Here,
new
category
of
1D
perovskite
ferroelectrics
(DFP)
2
SbX
5
(DFP
+
=
3,3‐difluoropyrrolidium,
X
−
I
,
Br
abbreviated
as
I‐1
and
Br‐2
)
with
twophase
transitions
(PTs)
reported.
The
first
low‐temperature
PT
mmm
F
mm
PT,
while
high‐temperature
counterintuitive
inverse
temperature
symmetry‐breaking
PT.
By
substitution
iodine
bromine,
Curie
(
T
c)
significantly
increases
from
348
K
to
374
.
Their
ferroelectricity
pyroelectricity
are
improved
P
s
value
1.3
4.0
µC
cm
−2
p
e
0.2
0.48
−1
for
),
their
optical
bandgaps
increased
2.1
2.7
eV.
A
critical
slowing
down
phenomenon
observed
dielectric
measurement
exhibits
ferroelastic
domain.
Structural
computational
analyses
elucidate
that
order‐disorder
movement
cations
distortion
chain
[SbX
]
2−
anions
skeleton
lead
semiconductor
properties
determined
by
anions.
findings
contribute
development
materials
PTs
provide
potential
applications
optoelectronic
field.
Advanced Materials,
Год журнала:
2023,
Номер
35(49)
Опубликована: Март 19, 2023
Abstract
Circularly
polarized
light
(CPL)
with
the
end
of
optical
vector
traveling
along
circumferential
trajectory
shows
left‐
and
right‐handedness,
which
transmits
chiral
information
to
materials
via
complicated
CPL–matter
interactions.
Materials
circular
dichroism
respond
CPL
illumination
selectively
differential
outputs
that
can
be
used
design
novel
photodetectors.
Racemic
or
achiral
compounds
under
go
through
photodestruction,
photoresolution,
asymmetric
synthesis
pathways
generate
enantiomeric
bias
activity.
By
this
strategy,
helical
polymers
inorganic
plasmonic
nanostructures
are
synthesized
directly,
their
intramolecular
folding
subsequent
self‐assembly
photomodulable
as
well.
In
aggregated
state
liquid
crystal
phase,
sense
dynamic
molecular
packing
is
sensitive
brought
by
CPL,
enabling
amplification
supramolecular
scale.
review,
application‐guided
strategies
CPL‐responsive
aimed
systematically
summarized
discussed.
Asymmetric
synthesis,
resolution,
property‐modulation
small
organic
compounds,
polymers,
nanoparticles,
assemblies
crystals
highlighted
based
on
important
developments
during
last
decades.
Besides,
applications
light–matter
interactions
including
detection
biomedical
also
referred.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(41)
Опубликована: Авг. 23, 2023
Due
to
the
pronounced
anisotropic
response
circularly
polarized
light,
chiral
hybrid
organic-inorganic
metal
halides
have
been
regarded
as
promising
candidates
for
application
in
nonlinear
chiroptics,
especially
second-harmonic
generation
circular
dichroism
(SHG-CD)
effect.
However,
designing
novel
lead-free
with
large
anisotropy
factors
and
high
laser-induced
damage
thresholds
(LDT)
of
SHG-CD
remains
challenging.
Herein,
we
develop
first
germanium
halide,
(R/S-NEA)3
Ge2
I7
⋅H2
O
(R/S-NGI),
systematically
investigated
its
linear
chiroptical
properties.
S-NGI
R-NGI
exhibit
(gSHG-CD
)
0.45
0.48,
respectively,
along
a
LDT
38.46
GW/cm2
;
these
were
highest
values
among
reported
halides.
Moreover,
effective
second-order
optical
coefficient
could
reach
up
0.86
pm/V,
which
was
2.9
times
higher
than
that
commercial
Y-cut
quartz.
Our
findings
facilitate
new
avenue
toward
halides,
their
implementation
applications.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(15)
Опубликована: Фев. 10, 2024
Abstract
Polar
materials
with
spontaneous
polarization
(
P
s
)
have
emerged
as
highly
promising
photocatalysts
for
efficient
photocatalytic
H
2
evolution
owing
to
the
‐enhanced
photogenerated
carrier
separation.
However,
traditional
inorganic
polar
often
suffer
from
limitations
such
wide
band
gaps
and
poor
transport,
which
hinders
their
efficiency.
Here,
we
rationally
synthesized
a
series
of
isostructural
two‐dimensional
(2D)
aromatic
Dion–Jacobson
(DJ)
perovskites,
namely
(2‐(2‐Aminoethyl)pyridinium)PbI
4
(2‐APDPI),
(3‐(2‐Aminoethyl)pyridinium)PbI
(3‐APDPI),
(4‐(2‐Aminoethyl)pyridinium)PbI
(4‐APDPI),
where
2‐APDPI
4‐APDPI
crystalize
in
space
groups
piezoelectric
constants
d
33
approximately
40
pm
V
−1
3‐APDPI
adopts
centrosymmetric
structure.
Strikingly,
‐facilitated
separation
carriers,
exhibit
3.9‐
2.8‐fold
increase,
respectively,
compared
3‐APDPI.
As
pioneering
study,
this
work
provides
an
approach
exploring
new
highlights
potential
promoting
evolution.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(13), С. 9272 - 9284
Опубликована: Март 22, 2024
Metal
halide
perovskites
(MHPs)
have
garnered
significant
attention
due
to
their
distinctive
optical
and
electronic
properties,
coupled
with
excellent
processability.
However,
the
thermal
characteristics
of
these
materials
are
often
overlooked,
which
can
be
harnessed
cater
diverse
application
scenarios.
We
showcase
efficacy
lowering
congruent
melting
temperature
(Tm)
layered
2D
MHPs
by
employing
a
strategy
that
involves
modification
flexible
alkylammonium
through
N-methylation
I-substitution.
Structural–property
analysis
reveals
I-substitution
play
pivotal
roles
in
reducing
hydrogen
bond
interactions
between
organic
components
inorganic
parts,
rotational
symmetry
number
cation
restricting
residual
motion
cations.
Additional
I···I
enhance
intermolecular
lead
improved
molten
stability,
as
evidenced
higher
viscosity.
The
discussed
this
study
exhibit
low
Tm
wide
melt-processable
windows,
e.g.,
(DMIPA)2PbI4
showcasing
98
°C
large
window
145
°C.
was
further
validated
when
applied
bromine-substituted
MHPs.
Lowering
enhancing
stability
hold
great
promise
for
various
applications,
including
glass
formation,
preparation
high-quality
films
photodetection,
fabrication
devices.
Advanced Functional Materials,
Год журнала:
2023,
Номер
33(26)
Опубликована: Март 24, 2023
Abstract
2D
chiral
hybrid
perovskites
have
recently
emerged
as
outstanding
semiconductor
materials.
However,
most
of
the
reported
limited
structural
types
and
contain
high
levels
toxic
lead,
which
severely
hinders
their
further
applications.
Herein,
by
using
a
mixed‐cation
strategy,
an
unprecedented
type
lead‐free
cluster‐based
double
perovskite
derivatives
are
successfully
obtained,
[(
R
/
S
‐PPA)
4
(IPA)
6
Ag
2
Bi
I
24
]·2H
O
(
1‐R
1‐S
),
n
‐BA)
2‐R
2‐S
)
‐PPA=
–1‐phenylpropylamine;
IPA=isopentylamine;
‐BA=
‐butylamine).
Their
inorganic
skeletons
linked
binuclear
{Bi
10
}
infinite
chain
{Ag
14
∞
,
in
bismuth
clusters
multiple
coordination
modes
(e.g.,
tetrahedral
AgI
octahedral
introduced
into
system
for
first
time.
This
introduction
induces
distortion
layer,
may
facilitate
transfer
chirality
from
cations
achiral
skeletons.
Further,
circular
dichroism
measurements
circularly
polarized
light
detection
confirm
inherent
optical
activities.
In
addition,
exhibits
ultralow
X‐ray
limit
129.5
nGy
s
−1
is
42‐fold
lower
than
that
demands
regular
medical
diagnosis
(5.5
µGy
).
study
provides
pathway
to
construct
novel
derivatives.
ACS Materials Letters,
Год журнала:
2023,
Номер
5(7), С. 1974 - 1981
Опубликована: Июнь 23, 2023
Green,
self-powered,
flexible,
and
tunable
features
have
been
greatly
desired
to
satisfy
the
increasing
demands
for
next-generation
photodetectors
sensors.
Here,
we
report
a
1D
lead-free
perovskite
ferroelectric
HDA-BiI5
(HDA
=
hexane-1,6-diammonium)
based
photodetector
showing
spectrally
selective
linear
polarized
light
response
due
unique
dichroic
conversion
behavior.
The
single
crystal
device
shows
an
orthogonal
reverse
of
polarization-sensitive
photocurrent
can
distinguish
linearly
in
different
wavelength
ranges
with
anisotropy
ratio
ω
about
1.37
at
405
nm,
1.00
490
1.17
530
nm.
Importantly,
achieves
ferroelectricity-driven
self-powered
detection
excellent
(∼1.28
nm)
high
detectivity
D*
5.3
×
108
Jones.
This
research
provides
pathway
design
future
integratable
photodetectors.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(31)
Опубликована: Июнь 6, 2023
Chiral
ferroelectric
crystals
with
intriguing
features
have
attracted
great
interest
and
many
point
or
axial
chirality
based
on
the
stereocarbon
been
successively
developed
in
recent
years.
However,
stereogenic
heteroatomic
never
documented
so
far.
Here,
we
discover
report
a
pair
of
enantiomeric
sulfur-chiral
single-component
organic
crystals,
Rs
-tert-butanesulfinamide
(Rs
-tBuSA)
Ss
(Ss
through
deep
understanding
chemical
design
molecular
crystals.
Both
enantiomers
adopt
chiral-polar
group
2
(C2
)
exhibit
mirror-image
relationships.
They
undergo
high-temperature
432F2-type
plastic
phase
transition
around
348
K.
The
ferroelectricity
has
well
confirmed
by
hysteresis
loops
domains.
Polarized
light
microscopy
records
evolution
ferroelastic
domains,
according
fact
that
is
both
ferroelastic.
very
soft
characteristics
low
elastic
modulus
hardness
reveals
their
excellent
mechanical
flexibility.
This
finding
indicates
first
stereosulfur
chiral
opening
up
new
fertile
ground
for
exploring
application
prospects.
Advanced Functional Materials,
Год журнала:
2023,
Номер
33(50)
Опубликована: Авг. 7, 2023
Abstract
2D
chiral
perovskite
has
greatly
boosted
the
development
of
optoelectronic
devices,
ranging
from
nonlinear
optics,
spintronics,
and
ferroelectrics
to
energy
harvesting
devices.
Despite
circularly
polarized
light
(CPL)
detection
based
on
been
achieved,
environmental
humidity‐,
ultraviolet
(UV),
temperature‐induced
structural
degradation
its
large
electro‐phonon
coupling
restrict
commercial
application.
Here,
this
study
first
realizes
polymerized
single‐crystal
films
by
combining
in
situ
cross‐linking
polymerization
with
space‐confined
crystallization
method.
Compared
uncross‐linked
perovskites,
cross‐linked
perovskites
exhibit
enhanced
crystallinity
lattice
rigidity,
yielding
high‐performance
photodetectors
a
maximum
anisotropy
factor
0.22,
responsivity
1.6
A
W
−1
,
detectivity
2.17
×
10
13
Jones.
In
addition,
flexible
extremely
high
mechanical
stability
are
also
realized
originating
polymer‐like
behavior
films.
This
opens
up
new
avenues
further
enhance
performance
portable
wearable
devices
perovskites.
Chemical Science,
Год журнала:
2024,
Номер
15(10), С. 3530 - 3538
Опубликована: Янв. 1, 2024
The
chirality-dependent
lattice
distortion
assisted
by
a
crown
ether
leads
to
an
intense
STEs
emission
along
with
CPL.
distinct
endows
the
Sb
halides
multi-stimuli-responsive
PL
behaviours
towards
excitation
wavelength
and
temperature.