Chemistry of Materials,
Journal Year:
2024,
Volume and Issue:
36(14), P. 6985 - 6993
Published: July 9, 2024
Structural
alteration
based
on
existing
molecules
is
an
effective
way
to
study
new
substances.
However,
a
limited
control
range
results,
especially
when
the
band
gaps
are
close
together,
from
difficulty
of
achieving
high
optical
anisotropic
enhancement
in
compounds
with
same
chemical
formula
as
comparable
behaviors
cations
and
anions
that
have
organic
inorganic
characteristics.
This
article
presents
methodical
investigation
highly
versatile
hydroxyfluorooxoborate
family
formulated
A2[B3O3F4(OH)]
(A
=
monovalent
cations),
which
coordinates
various
identical
heteroanionic
anion
[B3O3F4(OH)].
We
found
more
than
10
times
anisotropy
this
validated
anion–anion
tethered–heteroanion
interaction
for
tunable
anisotropy.
Furthermore,
it
noted
recently
discovered
member
[CN4H7]2[B3O3F4(OH)]
achieved
well-balanced
property
short
deep-ultraviolet
cutoff
edge
strong
birefringence.
Our
results
confirm
feasible
achieve
molecular
formulas.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
35(23)
Published: March 17, 2023
The
development
of
a
data-driven
science
paradigm
is
greatly
revolutionizing
the
process
materials
discovery.
Particularly,
exploring
novel
nonlinear
optical
(NLO)
with
birefringent
phase-matching
ability
to
deep-ultraviolet
(UV)
region
vital
significance
for
field
laser
technologies.
Herein,
target-driven
design
framework
combining
high-throughput
calculations
(HTC),
crystal
structure
prediction,
and
interpretable
machine
learning
(ML)
proposed
accelerate
discovery
deep-UV
NLO
materials.
Using
dataset
generated
from
HTC,
an
ML
regression
model
predicting
birefringence
developed
first
time,
which
exhibits
possibility
achieving
fast
accurate
prediction.
Essentially,
structures
are
adopted
as
only
known
input
this
establish
close
structure-property
relationship
mapping
birefringence.
Utilizing
ML-predicted
can
affect
shortest
wavelength,
full
list
potential
chemical
compositions
based
on
efficient
screening
strategy
identified.
Further,
eight
good
stability
discovered
show
applications
in
region,
owing
their
promising
NLO-related
properties.
This
study
provides
new
insight
into
identify
desired
high
performances
broad
space
at
low
computational
cost.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Feb. 1, 2024
ConspectusSecond-order
nonlinear
optical
(NLO)
materials
are
currently
a
hot
topic
in
modern
solid-state
chemistry
and
optics
because
they
can
produce
coherent
light
by
frequency
conversion.
Noncentrosymmetric
(NCS)
structure
is
not
only
the
prerequisite
for
NLO
but
also
challengeable
issue
tend
to
be
centrosymmetric
(CS)
terms
of
thermodynamical
stability.
Among
materials,
an
excellent
infrared
(IR)
candidate
should
simultaneously
meet
several
strict
key
conditions
including
large
coefficient,
high
laser-induced
damage
threshold
(LIDT),
phase-matchable
(PM)
behavior,
so
on.
Achieving
balance
between
effect
LIDT
difficult,
as
have
contradictory
requirements
chemical
bonds.
Considering
urgent
need
high-power
IR
laser
market
drawbacks
available
ones,
exploring
new
high-performance
crystals
necessary
while
challenging.
In
this
Account,
we
first
briefly
introduce
status
advancement
emphasize
criteria
candidate.
Then,
will
five
simple
methods
developed
us
discover
practical
candidates
through
understanding
composition–structure–NLO
performance
relationship.
(1)
A
rarely
investigated
system
with
compositions
new-type
crystals,
namely,
adducts
containing
S8
molecules,
developed.
Combining
chairlike
unit
other
units
van
der
Waals
forces
has
successfully
obtained
adducts.
(2)
The
main
trend
that
composition
more
diversified
complex,
expensive
chemically
active
alkaline
earth
metals
usually
introduced
counter
cations.
contrast,
research
on
systems
compositions,
structures,
low
costs
been
continuously
ignored.
binary
M2Q3
(M
=
Ga,
In;
Q
S,
Se)
family
rich
acentric
modifications
systematically
investigated,
all
exhibit
strong
SHG
effects
LIDTs.
(3)
We
proposed
concept
inducing
CS
structures
transformed
NCS
ones
partial
cation
substitution
design
novel
crystals.
huge
number
database
compared
it
attractive
method
apply
parents
obtain
potential
via
partial-substitution-induced
symmetry
breaking.
series
chalcogenides
performances
way.
(4)
NLO-active
rare
(RE)
chalcophosphates
systematically,
demonstrate
wonderful
comprehensive
properties.
(5)
created
mixed-anion
applications,
chalcogenide
borates.
Usually,
compounds
engender
synergistic
desired
Our
recent
progress
suggests
borates
although
study
still
its
infancy.
Finally,
state
current
problems
give
some
perspectives
their
future
development.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(11), P. 7868 - 7874
Published: March 8, 2024
Sulfate
crystals
are
often
criticized
for
their
low
birefringence.
The
small
anisotropic
SO4
group
is
becoming
the
biggest
bottleneck
hindering
application
of
sulfates
in
optical
functional
materials.
In
this
study,
we
report
a
new
method
to
significantly
enhance
birefringence
sulfates.
title
compound
increases
recording
0.542@546
nm,
which
larger
than
that
commercial
birefringent
crystal
TiO2
([email protected]
nm).
At
infrared
wavelength,
Hg4(Te2O5)(SO4)
can
be
up
0.400@1064
also
much
YVO4
(0.209@1064
addition,
it
has
wide
transparency
range,
high
thermal
stability,
and
excellent
environmental
making
potential
material.
features
novel
two-dimensional
layered
structure
composed
[Hg4(Te2O5)]2+
layers
separated
by
isolated
(SO4)2–
tetrahedra.
This
was
designed
introducing
highly
selective
cation
tellurite
sulfate
system.
valence
coordination
cations
connect
with
groups
only,
structure.
steric
repulsive
action
tetrahedra
may
regulate
linear
lone
pair
arranged
way
favors
large
proven
theoretical
calculations.
PAWED
studies
showed
originated
from
synergistic
effect
(Hg2O2)2–,
(Te2O5)2–,
units,
contribution
ratio
42.17,
37.92,
19.88%,
respectively.
Our
work
breaks
limitation
opens
possibilities
as
crystals.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: April 5, 2024
Abstract
Divalent
lanthanide
inorganic
compounds
can
exhibit
unique
electronic
configurations
and
physicochemical
properties,
yet
their
synthesis
remains
a
great
challenge
because
of
the
weak
chemical
stability.
To
best
our
knowledge,
although
several
monoxides
epitaxial
thin
films
have
been
reported,
there
is
no
chemically
stable
crystalline
divalent
chalcogenide
synthesized
up
to
now.
Herein,
by
using
octahedra
coupling
tetrahedra
single/double
chains
construct
an
octahedral
crystal
field,
we
La(II)-chalcogenide,
LaMg
6
Ga
S
16
.
The
nature
La
2+
cations
be
identified
X-ray
photoelectron
spectroscopy,
absorption
near-edge
structure
electron
paramagnetic
resonance,
while
stability
confirmed
differential
thermal
scanning,
in-situ
variable-temperature
powder
diffraction
series
solid-state
reactions.
Owing
particular
characteristics
(5
d
1
),
displays
ultrabroad-band
green
emission
at
500
nm,
which
inaugural
instance
La(II)-based
demonstrating
luminescent
properties.
Furthermore,
as
crystallizes
in
non-centrosymmetric
space
group,
P
−6,
it
second-harmonic
generation
(SHG)
active,
possessing
comparable
SHG
response
with
classical
AgGaS
2
In
consideration
its
wider
band
gap
(
E
g
=
3.0
eV)
higher
laser-induced
damage
threshold
(5×AgGaS
also
promising
nonlinear
optical
material.
Materials Horizons,
Journal Year:
2022,
Volume and Issue:
10(2), P. 619 - 624
Published: Nov. 25, 2022
Infrared
nonlinear
optical
(IR-NLO)
materials
with
wide
band
gaps
are
important
for
generating
high-power
laser
light
modern
technologies.
Herein,
a
gap
IR-NLO
material,
Rb2CdSi4S10,
was
rationally
designed
and
fabricated
by
introducing
NLO-active
[Si4S10]
T2-supertetrahedron
(ST)
into
the
quaternary
sulfide
system.
The
Rb2CdSi4S10
shows
largest
(4.23
eV)
among
chalcogenide
reported,
which
results
in
high
laser-induced
damage
threshold
(LIDT)
of
∼5
×
AgGaS2
(AGS)
at
1064
nm.
At
same
time,
it
has
moderate
second-harmonic
generation
(SHG)
response
(0.6
AGS).
Based
on
statistical
analyses,
is
first
compound
to
be
discovered
AI2BIICIV4QVI10
family,
also
Si-rich
material
T2-supertetrahedra.
indicate
that
promising
new
T2-ST
unit
could
used
exploration
excellent
performances.
Small,
Journal Year:
2023,
Volume and Issue:
19(46)
Published: July 20, 2023
Hg-based
chalcogenides,
as
good
candidates
for
the
exploration
of
high-performance
infrared
(IR)
nonlinear
optical
(NLO)
materials,
usually
exhibit
strong
NLO
effects,
but
narrow
bandgaps.
Herein,
an
unprecedented
wide
bandgap
IR
material
Zn2
HgP2
S8
(ZHPS)
with
diamond-like
structure
is
rationally
designed
and
fabricated
by
a
tetrahedron
re-organization
strategy
aid
property
predictions.
ZHPS
exhibits
3.37
eV,
which
largest
one
among
reported
chalcogenide
materials
first
breaks
3.0
eV
"wall"
in
this
system,
resulting
high
laser-induced
damage
threshold
(LIDT)
≈2.2
×
AgGaS2
(AGS).
Meanwhile,
it
shows
large
response
(1.1
AGS),
achieving
balance
between
(≥3.0
eV)
effect
(≥1
AGS)
excellent
material.
DFT
calculations
uncover
that,
compared
to
normal
[HgS4
]n
,
highly
distorted
]d
tetrahedral
units
are
conducive
generating
bandgap,
can
be
attributed
s-p
hybridization
Hg─S
bonding
gives
some
insights
into
design
chalcogenides
properties
based
on
tetrahedra.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(16)
Published: Feb. 20, 2023
Traditional
infrared
(IR)
nonlinear
optical
(NLO)
materials
such
as
AgGaS2
are
crucial
to
key
devices
for
solid-state
lasers,
however,
low
laser
damage
thresholds
intrinsically
hinder
their
practical
application.
Here,
a
robust
strategy
is
proposed
unbiased
high-throughput
screening
of
more
than
140
000
explore
novel
IR
NLO
with
high
thermal
conductivity
and
wide
band
gap
which
intrinsic
threshold.
Via
our
strategy,
106
compounds
desired
gaps,
coefficients
screened
out,
including
8
nitrides,
68
chalcogenides,
in
Sr2
SnS4
synthesized
verify
the
reliability
process.
Remarkably,
nitrides
much
higher
that
e.g.,
5×AgGaS2
(5.13
W/m
K)
ZrZnN2
,
indicating
could
be
long-neglected
system
materials.
This
provides
powerful
tool
searching
conductivity.
Advanced Optical Materials,
Journal Year:
2023,
Volume and Issue:
11(16)
Published: May 17, 2023
Abstract
The
exploration
of
antilaser
damage
wide
bandgap
infrared
(IR)
nonlinear
optical
(NLO)
materials
is
urgent
but
challenging.
Herein,
by
introducing
the
idea
fluorination
into
chalcogenides,
a
IR
NLO
material
Na
3
SiS
F
with
unprecedented
[SiS
F]
tetrahedra
designed
and
synthesized.
shows
4.75
eV
(the
largest
one
in
reported
quaternary
metal
chalcogenides),
resulting
high
laser
induced
threshold
≈5
×
AgGaS
2
(AGS).
Meanwhile,
compound
has
moderate
response
(≈0.3
×AGS)
phase‐matching
behavior,
large
birefringence
(0.15@1064
nm),
transparent
region.
introduction
fluorine
breaks
structural
symmetry
broadens
highest
occupied
molecular
orbital‐lowest
unoccupied
orbital
(HOMO‐LUMO)
gap,
polarizability
anisotropy,
hyperpolarizability
Si–S
tetrahedral
unit.
results
indicate
that
promising
for
high‐power
application
open
an
avenue
design
new
based
on
NLO‐active
x
4−
]
(
=
1,
2,
3)
mixed
anionic
group.
Small,
Journal Year:
2023,
Volume and Issue:
19(39)
Published: May 28, 2023
Oxides
are
emerging
candidates
for
mid-infrared
(mid-IR)
nonlinear
optical
(NLO)
materials.
However,
their
intrinsically
weak
second
harmonic
generation
(SHG)
effects
hinder
further
development.
A
major
design
challenge
is
to
increase
the
coefficient
while
maintaining
broad
mid-IR
transmission
and
high
laser-induced
damage
threshold
(LIDT)
of
oxides.
In
this
study,
it
reported
on
a
polar
NLO
tellurite,
Cd2
Nb2
Te4
O15
(CNTO),
featuring
pseudo-Aurivillius-type
perovskite
layered
structure
composed
three
types
active
groups,
including
CdO6
octahedra,
NbO6
TeO4
seesaws.
The
uniform
orientation
distorted
units
induces
giant
SHG
response
that
≈31
times
larger
than
KH2
PO4
,
largest
value
among
all
metal
tellurites.
Additionally,
CNTO
exhibits
large
band
gap
(3.75
eV),
wide
transparency
window
(0.33-14.5
µm),
superior
birefringence
(0.12@
546
nm),
LIDT
(23
×
AgGaS2
),
strong
acid
alkali
resistance,
indicating
its
potential
as
promising
material.