Understanding the Structural Dimensionality

Determined Band Gap Evolution in An+1BnX3n+1

Ruddlesden-Popper Perovskites: A Unified
Picture

Yajun Zhang,∗,†,‡ M. P. K. Sahoo,¶ Yunting Liang,§ and Gang Tang∥

†Key Laboratory of Mechanics on Disaster and Environment in Western China, Ministry

of Education of China, Lanzhou University, Lanzhou, Gansu 730000, People’s Republic of
China
‡Department of Mechanics and Engineering Sciences, College of Civil Engineering and
Mechanics, Lanzhou University, Lanzhou, Gansu 730000, People’s Republic of China
¶Department of Physics, Veer Surandra Sai University of Technology, Burla, Odisha, India
§School of Energy Engineering, Huanghuai University, Zhumadian 463000, Henan,
People’s Republic of China
∥Theoretical Materials Physics, Q-MAT, CESAM, Université de Liège, B-4000 Liège,
Belgium

E-mail: zhangyajun@lzu.edu.com

Abstract

Dimensionality engineering in An+1 Bn X3n+1 Ruddlesden-Popper (RP) perovskites

has recently emerged as a promising tool to tune band gap for improving optoelectronic

properties. However, the evolution of band gap is material-dependent, distinguishing

1
 the effects of different factors, and unraveling previously unknown and overlooked fac-

tors are urgently needed to guide the rational design of high-performance materials.

Through first-principles calculations, we perform a systematical investigation on RP

oxide, chalcogenide, and halide perovskites. The results reveal that in addition to

confinement effect and change of octahedral rotation motions/amplitude, interfacial

rumpling and change of A-site cation coordination number also determine the evolu-

tion of the band gap. More importantly, we emphasize that the evolution of band

gap in RP perovskite is not material family dependent. Instead, B-site frontier orbital

type (s, p and d) and bandwidth, A-site cation, interfacial rumpling, and structural

distortions simultaneously determine the evolution of band gap. These insights enable

a complete and deeper understanding of various experimental observations.

Ruddlesden-Popper perovskites (RP) with the general formula An+1 Bn X3n+1 are currently
highly attractive systems for technological applications in optoelectronic devices such as
solar cells, 1–4 light-emitting diodes, 5–8 and field-effect transistors. 9–11 Compared with bulk
ABX3 perovskites, one of the tremendous advantages of RP perovskites is the degree of
freedom of dimensionality n, which becomes an ideal platform for tuning the band gap, orbital
energy level, chemical-stability, and charge transport. 2,12–23 In particular, band gap directly

2
affects the practical application and efficiency of RP perovskites in optoelectronic devices,
which motivates extensive research efforts for band gap modulation through dimensionality
engineering. 2,12–18
Nevertheless, the evolution trend of the band gap is strongly material-dependent. Dif-
ferent studies have reported both band gap increase and decrease as n decreases. For
example, with the decrease of n, the band gaps of Srn+1 Tin O3n+1 , 12 Can+1 Tin O33n+1 , 13
(PE)n−1 (MA)2 Pbn I3n+1 2 are experimentally observed to be increased, while recently Li et
al., proposed that the band gap of Ban+1 Zrn S3n+1 is decreased. 14
Although enormous prior studies seem to provided satisfactory explanation for the evo-
lution of band gap, 2,12–18 however, the typical focus is on one or few compounds. Besides,
a global picture suitable for all the RP compounds is yet to be reported. In addition, the
driving forces behind are either ascribed to quantum confinement or octahedral rotation, it
is natural to wonder whether there are other key factors that strongly affect the evolution
of band gap ?
In hybrid halide perovskites (PE)n−1 (MA)2 Pbn I3n+1 , the author concluded that the tun-
able band gap resulted from the quantum confinement effect. 2 In terms of all-inorganic RP
perovskites, Li et al., nicely explained the band gap evolution of Ban+1 Zrn S3n+1 by consider-
ing both the effect of quantum confinement and rotation. 14 Further comparing with oxides
(Srn+1 Tin O3n+1 ), halides ((PE)n−1 (MA)2 Pbn I3n+1 ), they argue that in contrast to the RP
oxides and halides, the band gap of the RP chalcogenides evolve differently with the thick-
ness. 14 Is this conclusion true for all the families of RP oxides, halides, and chalcogenides?
Comparing only one compound in each family maybe inadequate to get a general conclusion.
For halide perovskite CsSnBr3 , the octahedral rotation is also significantly decreased
from bulk Pnma phase to RP P 42 /mnm Cs3 Sn2 Br7 similarly with BaZrS3 , while the band
gap increases instead of decreases. 24 So, what is the dominant physics that differentiates
two materials? Additionally, there are still many fundamental issues regarding the evolution
of the band gap which are mandatory to be clarified to provide convincing guidelines for

3
material design. For example, what are the effects of orbital type (s, p and d) at the band
edge, interface effect, and the change of coordination number of A-site cations? What are the
minimal factors needed to be considered to fully assess the evolution of the band gap? how
each factor affects the bandwidth and energy level of orbitals and how do such modifications
influence the band gap?
The objective of the present work is to perform a comprehensive analysis of the dimensionality-
band gap relationship in RP perovskites by first-principles calculations. Through a compar-
ative study of RP oxide, chalcogenide and halide perovskites, we reveal that the evolution of
the band gap strongly depends on not only the confinement effect and change of rotation dis-
tortions but also on the type of orbital at the band edge, interfacial rumpling, and change of
A-site cation coordination number. The role of each factor is disentanged and a complete and
consistent description of the dimensionality-dependent band gap is achieved. Importantly,
the sensitivity of the band gap on these factors strongly depends on the orbital composition
at the band edge, thus resulting in different evolution trends in a different family of materials.
B-site p and s orbitals at the band edge are highly sensitive to the confinement effect, thus,
confinement effect in RP halide perovskites and An+1 Snn O3n+1 (A = Ca, Sr, and Ba) domi-
nantly increases the band gap as dimensionality decreases. For RP chalcogenide perovskites,
there is delicate competition between the confinement effect and the decrease of rotation
amplitude induced by the competition with rumpling. As the strength of rotation-rumpling
competition and rotation reduction amplitude in different RP chalcogenide perovskites are
different, compounds in the RP chalcogenide perovskites exhibit different evolutionary trends
of the band gap. The situation is more complex in RP oxide perovskites since the A cation
in some compounds also contributes to the frontier orbitals in the parent ABO3 perovskites,
and the band edge of the A-site d orbitals for these compounds gradually decreases as the
dimensionality decreases, which plays an opposite role with confinement effect. Additionally,
rumpling modified B-O bond length in a few compounds could also affect the position of
the band edge. Therefore, the combined effects of confinement effect, orbital type, lattice

4
Figure 1: Band gap of the ground state structure for (a) RP oxide perovskites and (b) RP
chalcogenide and halide perovskites.

distortion, A-site cation, and rumpling are essential to fully understand the change of band
gap in RP oxide perovskites.
Band gap evolution in RP perovskites. To give a more general analysis of band gap
evolution in RP perovskites, compounds with different i) family (oxides, chalcogenides and
halides); ii) B-site atom orbital type (s, p and d) at the band edge; iii) B-site atom bandwidth
of frontier orbitals; iv) A-X ionic bond strength; v) crystal structural (distorted or undis-
torted) are selected to fully consider all the possible factors that affect the band gap. The
band gap of ABX3 bulk material, RP A2 BX4 , and A3 B2 X7 phases with their lowest energy
structures (see Table S1) are compared in Figure 1. Different compositions show a strong
difference in the evolution of band gap and the evolution trend cannot be simply classified
by material family. It should be noted that among the above RP compounds, Sr3 Ti2 O7 , 12
Ca3 Ti2 O7 , 13 Ba2 ZrS4 , 14 Ba3 Zr2 S7 14 have been synthesized, and the evolution trend of band
gap in Figure 1 are consistent with all the experimental results, which guarantees the ac-
curacy of our calculations and also reflects the capabilities of the Perdew-Burke-Ernzerhof
exchange-correlation functional revised for solids (PBEsol) functional to correctly capture
the band gap evolution.

5
Figure 2: Band gap of the pseudocubic phase, RP A3 B2 X7 and A2 BX4 phases artificially
built from the pseudocubic phase for (a) oxide perovskites and (b) chalcogenide and halide
perovskites.

Although the band gap evolution is strongly material dependent, we can still find some
general features: i) halide perovskite exhibit increased band gap with decreasing n; ii) the
band gap of oxides with Sn at B-site increases almost monotonically as n decreases. The
evolution trends of all the other compounds are more complex and exhibit inconsistent
behaviors, which may be determined by the delicate balance of different factors. To clarify
the underlying microscopic mechanism behind it, we perform a careful investigation in the
following to rationalize the role of different factors.
Impact of confinement effect. It is well known that one of the main effects of dimen-
sionality reduction is the confinement effect, which restricts out-of-plane electron movement,
decreases the bandwidth of orbitals and trends to increase the band gap. To investigate the
confinement effect, we start from the pseudocubic phase of ABX3 compounds, and then com-
pare the band gap of the pseudocubic phase, RP A3 B2 X7 and A2 BX4 phases artificially built
from the pseudocubic phase without relaxation. The corresponding band gap is displayed
in Figure 2. Several interesting phenomena could be found by comparing Figure 1 and Fig-
ure 2: i) the evolution trend of band gap for Srn+1 Tin O3n+1 , Ban+1 Zrn O3n+1 , Can+1 Zrn O3n+1 ,

6
Can+1 Hfn O3n+1 , Ban+1 Snn O3n+1 , Srn+1 Snn O3n+1 , Csn+1 Snn I3n+1 , Csn+1 Snn Br3n+1 , Csn+1 Pbn I3n+1
and Csn+1 Pbn Br3n+1 is consistent; ii) the change of band gap is inconsistent for Ban+1 Hfn O3n+1 ,
Srn+1 Zrn O3n+1 , Can+1 Snn O3n+1 , Srn+1 Zrn S3n+1 , Srn+1 Hfn S3n+1 , Can+1 Zrn S3n+1 and Can+1 Hfn S3n+1 ;
iii) for Ban+1 Zrn S3n+1 , Ban+1 Hfn S3n+1 , the band gap evolutions even show opposite trend. If
we only consider the effect of dimensionality, it seems that the band gap may continuously
increase, gradually decrease or first increase and then decrease across ABX3 → A3 B2 X7 →
A2 BX4 series. From the above results we can reach two conclusions: i) confinement effect
remarkably increases the band gap of some compounds, especially these contain s and p
orbital in the B-site atom; ii) confinement effect is insufficient to account for the evolution
of band gap for all the RP An+1 Bn X3n+1 perovskites and factors beyond confinement effect
need to be considered to fully understand the dimensionality effect.
A-X ionic bond effect. Note that in the results of Figure 2, we use artificial high-symmetry
structures which rules out the effect of lattice distortions like octahedral rotation and lattice
strain which are common factors that influence the electronic structure. Despite the band
gap of halide and chalcogenide perovskites gradually increases as n decreases due to the
confinement effect, the evolutions of the band gap in different perovskite oxides are different.
To shed further insight into the other factor beyond confinement effect, lattice distortions and
lattice strain that affects the band gap, we compare the projected density of state (PDOS) of
a set of representative ABX3 compounds and their corresponding A2 BX4 RP phase including
SrSnO3 , CsSnBr3 , SrZrS3 , SrTiO3 and SrZrO3 . These compounds are selected not only due
to their different band gap evolution, but also because they have different electron orbitals
composition.

7
Figure 3: PDOS of the pseudocubic phase and RP A2 BX4 phase artificially built from the
pseudocubic phase for (a) SrSnO3 and Sr2 SnO4 , (b) CsSnBr3 and Cs2 SnBr4 , (c) SrZrS3 and
Sr2 ZrS4 , (d) SrTiO3 and Sr2 TiO4 and (e) SrZrO3 and Sr2 ZrO4 .

Comparing the PDOS shown in Figure 3, one can see an obvious and interesting phe-

8
nomenon: Srn Zrn+1 O3n+1 with unusual band gap evolution (band gap decreases as dimen-
sionality n decreases) trends to have notable contribution from A-site atomic orbital at the
conduction band minimum (CBM) in the ABX3 phase, and the dominant states at the CBM
have changed from the Zr d electron in SrZrO3 to Sr d electron in Sr2 ZrO4 . A similar phe-
nomenon has also been found in all the other compounds with unusual band gap evolution
(see Figure S1). However, the compounds with common band gap evolution (band gap in-
creases as dimensionality n decreases) have ignorable A-site atomic orbital at the CBM in
both the ABX3 and A2 BX4 phases.
The reason behind the unusual band edge change of Sr2 ZrO4 can be understood from
the change of A-X ionic bond strength. When ABX3 perovskite forms RP structure, the
coordination number of A-site cations at the interface is reduced from 12 to 9, which reduces
n
zi2 (z is the charge on the
P
the strength of A-X ionic bond since ionic bond strength I ∝
i
ions, n represents the number of ions). For the ABX3 phase with non-negligible A-site ionic
contribution at the CBM, the decreased ionic bond strength further enhances the hopping
of electrons and the A-site orbital bandwidth, which as a consequence leads to the decrease
of the band gap. To conclude, despite the A-site ion is typically passive and would not affect
the band gap evolution of RP compounds, it can indeed play a direct role in the band edge of
some compounds and the dimensionality effect controlled band gap evolution is determined
by both confinement effect and A-X ionic bond strength.
Rotation effect. In RP perovskites, beyond the role of confinement and A-X ionic bond,
the amplitude of the B-X-B bond angle is another key indicator of the electron hopping and
orbital hybridization, therefore, dramatically altering the band gap. Typically, the bond an-
gle is controlled by octahedral rotation, and the larger the degree of octahedral rotation, the
smaller the bond angle and the larger the band gap. 25,26 Therefore the evolution of rotation in
the RP series becomes another factor controlling the band gap. To facilitate the understand-
ing of the impact of rotation or bond angles, we start from the cubic phase and compare the
PDOS of structures by fixing in-phase rotation (P 4/mbm phase) or out-of-phase tilt (Imma

9
Figure 4: PDOS of the pseudocubic phase (middle), pseudocubic phase with tilt distor-
tion (upper), and pseudocubic phase with rotation distortion (lower) for (a) CaSnO3 , (b)
CsSnBr3 , and (c) BaZrS3 .

phase) that reduces in-plane or out-of-plane B-X-B angle by 20◦ . CaSnO3 , CsSnBr3 and
BaZrS3 with different orbitals at the conduction band are selected for comparison.
It is obvious from Figure 4 that the behaviors of all the compounds share the same feature:
the bandwidth of s or p orbital right below the Fermi level is narrowed which directly lowers
the valence band maximum (VBM), in contrast, the bandwidth and energy level of orbital
at the CBM are weakly modified leading to the increase of band gap. The reduction of
bandwidth can be rationalized by the reduced B-X hybridization caused by the decrease of
the B-X-B bond angle and is a common feature in perovskites.
Interfacial rumpling effect. Finally, we emphasize that interfacial rumpling is another
structural factor that has a decisive effect on the band gap. On the one hand, rumpling

10
Figure 5: (a) Evolution of the energy with respect to in-phase rotation (X2+ ) and out-of-phase
tilt (X3− ) with and without the fixing of initial rumpling in (a) Sr3 Zr2 S7 and (b) Sr2 ZrS4 . (c)
The comparison of PDOS of in Ba2 ZrO4 without (lower) and with (upper) rumpling. The
PDOS are aligned with respect to the energy level of the Ba s orbital of the phase without
rumpling.

notably suppresses the rotation in RP perovskites as demonstrated in our previous work, 27

which as a result significantly reduces the band gap in an indirect way. On the other hand,
rumpling also changes the A-O and B-O bond length, thus directly affecting the orbital
hybridization between cation and anion.
To evaluate the actual contribution of rumpling, we firstly focus on the structural prop-
erty, namely the competition between rumpling and rotation. Figure 5a and 5b shows the
energy potential surface (PES) of Srn+1 Zrn S3n+1 with and without initial rumpling for in-
phase rotation and out-of-phase tilt, respectively. It is evident that the energy gain and mode

11
amplitude of the two modes are reduced with the appearance of rumpling. The double-well
potential-energy remains for both rotation and tilt in Sr3 Zr2 S7 and Sr2 ZrS4 leading to the
ferroelectric Cmc21 ground state for Sr3 Zr2 S7 and P bcn state for Sr2 ZrS4 . For Ba3 Zr2 S7 ,
we have demonstrated that the in-phase rotation is completely suppressed resulting in the
P 42 /mnm ground state. 27
We then consider Ba2 ZrO4 as a model system to investigate the direct effect of rumpling
on the electronic structure. Figure 5c displays a comparison of the PDOS of Ba2 ZrO4 with
and without rumpling, one can see that rumpling has a non-negligible effect on the band
edge at both valence and conduction bands. Detailed PDOS analysis indicates that rumpling
splits the triply degenerate t2g conduction band originating from the elongation of the out-
of-plane Zr-O bond. Moreover, the band edge of O-p orbitals at the VBM undergoes a
downshift giving rise to a slight increase in the band gap.
Rationalizing band gap evolution in RP perovskites. Having provided a completely un-
derstanding of the role of main factors affecting the band gap of RP compounds, we shift
our attention to rationalize recent experimental observations based on our knowledge.
Recent work shows that the band gap of RP Ban+1 Zrn S3n+1 decreases as n decreases,
which is attributed to the significant decrease in octahedral rotation. 14 The optimized band
gaps of 1.28 eV ( n= 1) and 1.33 eV (n = 2) not only makes RP Ban+1 Zrn S3n+1 promising for
efficiency enhancement as solar cells but also suggests engineering rotation as an alternative
and effective way to modulate the band gap in RP system. They further point out that the
band gap of Srn Zrn+1 S3n+1 and Srn Hfn+1 S3n+1 also decreases with decreasing n. However, as
shown in Figure 1, we found that their band gap first increases (n = 2) and then decreases
(n = 1) but still comparable with their parent ABS3 compounds. The difference in our
results is not originating from the error of DFT calculations, but different structures used
for calculations. For Sr3 Zr2 S7 , we use the ground state Cmc21 phase while Li et al., 14 use
the higher symmetry P 42 /mnm phase and we use the ground state P bca (a− a− c+ ) phase
for Sr2 ZrS4 instead of the high-symmetry I4/mmm phase. The comparison of total energy

12
 Figure 6: The PDOS of (a) Ban Zrn+1 S3n+1 , (b) Srn Zrn+1 S3n+1 , and (c) Csn Snn+1 Br3n+1 .

in different phases is displayed in Table S2.

To give a further insight into the competing effect of rotation and confinement effect,
and rationalize the nonsystematic evolution of band gap in the RP chalcogenides series, we
perform a comprehensive structural and electronic analysis on BaZrS3 and SrZrS3 and their
corresponding RP phases. Figure 6a and 6b compares the PDOS of BaZrS3 and SrZrS3 in
the ABX3 bulk and RP phases. It is apparent that the valence bands are primarily composed
of S p orbitals and the conduction bands are dominant by the Zr d orbitals. As shown in
Figure 3a, the bandwidth of RP I4/mmm Ba2 ZrS4 is notably narrowed and the VBM shifts
to a lower energy level compared with P m3m BaZrS3 owning to the confinement effect. Here
similar narrowing of S p bandwidth is also observed in RP P 42 /mnm Ba3 Zr2 S7 relative to
P nma BaZrS3 . However, due to the suppression of in-phase rotation by the competition with

13
rumpling in the Ba3 Zr2 S7 , the band edges of S p and Zr d orbitals increase to a higher energy
level resulting from the increased hybridization. There is also a strong orbital polarization
of t2g and eg orbitals at the conduction band since dyz , dzx , and d3z2 −r2 orbitals are more
confined. Additionally, the enhanced hybridization between in-plane S p and Zr d orbitals
leads to the increase in the bandwidth of dxy and dx2 −y2 orbitals. The strong boarding of dxy
and dx2 −y2 orbitals together with the red shift of the S p orbital eventually results in a global
decrease of the band gap. Decreasing the perovskite layer to only one unit-cell thick, the out-
of-plane tilt is further suppressed leading to the further straightening of the in-plane Zr-S-Zr
bond angle. Consequently, the bandwidth of dxy and dx2 −y2 orbitals is further increased and
the band edge shifts to a lower energy level accompanied by the further decrease of the band
gap. We can thus conclude that the change of bandwidth and energy level of dxy , dx2 −y2 , and
S p orbitals are responsible for the decrease of the band gap in Ban+1 Zrn S3n+1 as n decreases.
In terms of Srn+1 Zrn S3n+1 , the in-phase rotation is slightly reduced from the P nma SrZrS3
phase to the Sr3 Zr2 S7 phase, and the in-plane Zr-S-Zr bond angle decreases by only 3◦ which
is much smaller of 20◦ in Ba3 Zr2 S7 . Thus, the effect of decreased rotation on the band gap
is much smaller than the confinement effect, which eventually leads to a increase in the
band gap. However, the in-phase rotation is substantially suppressed when n = 1, which
significantly decreases the in-plane Zr-S-Zr bond angles by 18◦ . As a result, the effect of
decreased rotation on the bandwidth of dxy and dx2 −y2 orbitals is strongly strengthened and
consequently the band gap experiences a notable decrease from Sr3 Zr2 S7 to Sr2 ZrS4 .
All in all, our results confirm that the band gap evolution is determined by the combined
effect of rotation amplitude and confinement effect. However, despite BaZrS3 and SrZrS3
belonging to the same family and sharing the same composition of VBM and CBM, we
highlight that their band gap evolution in the RP phase is obviously different derives from
their strong difference in the amplitude of initial rotation in the AZrS3 phase and strength of
competition between rotation and rumpling. We thus hope experiments could reevaluate the
band gap evolution in Srn+1 Zrn S3n+1 , and explore the similarities and differences between

14
Ban+1 Zrn S3n+1 and Srn+1 Zrn S3n+1 .
We further rationalize the band gap evolution of Csn+1 Snn Br3n+1 . Although the evolu-
tion of rotation motions within the CsSnBr3 -Cs3 Sn2 Br7 -Cs2 SnBr4 series is exact the same
as that of Ban+1 Zrn S3n+1 , Csn+1 Snn Br3n+1 shows a monotonically increase of band gap 24
rather than the continuous decreasing trend observed in Ban+1 Zrn S3n+1 . 14 The PDOS of
Csn+1 Snn Br3n+1 is displayed in Figure 6c, comparing the PDOS with Ban+1 Zrn S3n+1 , we
see a strong downshift of the VBM. Despite the decreased in-plane rotation should enhance
the bandwidth and energy level of the Br s orbital as found in the Ban+1 Zrn S3n+1 , the Br
s orbital is more sensitive to the confinement effect than the S p orbital. As a result, the
confinement effect decreased bandwidth of Br s orbital overwhelms the effect of increased
hybridization. Moreover, the band edge of the Sn p orbital is increased, these two factors are
responsible for the increased band gap. Therefore, the different composition and sensitivity
of orbitals to the confinement effect drive the different evolution of band gap in two families
of compounds.
Finally, we carried out a comparative investigation of RP oxides to rationalize the differ-
ence in the band gap evolution for different compounds. We firstly focus on the fundamental
difference between Srn Tin+1 O3n+1 and Ban Hfn+1 O3n+1 , both of which have no rotation dis-
tortion. From Figure 1, we see that although isostructural to Srn Tin+1 O3n+1 , the band gap
evolution of Ban Hfn+1 O3n+1 is very different. Srn Tin+1 O3n+1 display a monotonically in-
crease of band gap with decreasing n, while Ban Hfn+1 O3n+1 exhibit first increase and then
decrease of band gap as n decreases.
In order to unveil the physical origin behind their difference, we compare the PDOS of
two compounds with respect to different n values. A clear difference between the electronic
structures of two compounds arises from the composition of CBM: the CBM of STO consist
mainly of the d orbitals of Ti, while the Ba d orbitals in Ban Hfn+1 O3n+1 also make a significant
contribution to the CBM. Moreover, the band edge of Ba d orbitals becomes even lower than
the Hf d orbitals for n = 1, which should be responsible for the unusual decrease of band

15
 Figure 7: The PDOS of (a) Srn Tin+1 O3n+1 , (b) Ban Hfn+1 O3n+1 , and (c) Srn Zrn+1 O3n+1 .

gap as n decreases. Their different behaviors are closely correlated to the strength of A-X
ionic bond as we mentioned above, the Ba-O ionic bond is more sensitive to the change of
coordination number, and the decrease of ionic bond strength as n decreases directly leads
to the broadening of the bandwidth of Ba d orbitals, which eventually results in the shift of
Ba d orbitals to a lower energy level. The above results unambiguously confirm that A-site
orbitals could also have a tremendous effect on the band gap in RP compounds.
Now we discuss the origin of unusual band gap evolution in Srn Zrn+1 O3n+1 . We found
that Srn Zrn+1 O3n+1 resembles the structural evolution of Srn Zrn+1 S3n+1 as n varies and expe-
riences a P nma-Cmc21 -P 42 /mnm phase transitions from SrZrO3 , to Sr3 Zr2 O7 and Sr2 ZrO4 .
The change of in-plane Zr-O-Zr bond angle also shows a marked resemblance to that of
Zr-S-Zr in Srn Zrn+1 S3n+1 . Consequently, the similar argument for the uncommon band gap

16
evolutions in Srn Zrn+1 S3n+1 can also be applied to Srn Zrn+1 O3n+1 : For n=2 in which in-phase
rotation only slightly decreases, the band gap is dominated by the confinement effect. With
the significant decrease of in-phase rotation in Sr2 ZrO4 , the dxy orbital is strongly broadened
and its band edge shifts to a much lower energy level which is then accompanied by the
narrowing of the band gap.
In summary, the dimensionality-band gap connection in RP oxide, chalcogenide and
halide perovskites are compared and we highlight that the combined effect of well-known con-
finement effect and structural evolution and previously overlooked rumpling and A-cation
is the foundation to develop a unified and coherent picture of band gap evolution in RP
perovskites. Our work has established the role of each factor and provided a thorough
understanding of the structural and electronic properties. The results could therefore com-
plement the understanding of band gap engineering in RP perovskites and is of great benefit
for rationalizing and controlling the band gap.

Methods

First-principles calculations were performed using density functional theory (DFT) with the
PBEsol functional 28 as implemented in the Vienna ab initio simulation package (VASP). 29,30
We use a plane-wave cutoff of 600 eV and 8 × 8 × 6 Monkhorst-Pack k-point mesh 31 for
√ √
2 × 2 × 2 supercells. During the structural optimizations, the lattice parameters and
internal ionic coordinates are fully relaxed until the total energy and Hellmann-Feynman
forces on each atom are converged to less than 10−7 eV and 10−3 eV/Å, respectively. The
symmetry analysis and modes amplitudes are performed by the ISODISTROPY. 32,33 If not
mentioned, the PDOS are aligned with respect to the energy level of the s orbital of the
A-site cation in the ABX3 reference phase.

17
References

Acknowledgement

This work was financially supported by the Initial Scientific Research Fund of Lanzhou
University for Young Researcher Fellow (No.561120206). The calculations are supported by
the Center for Computational Science and Engineering of Lanzhou University and Southern
University of Science and Technology.

Supporting Information Available

This will usually read something like: “Experimental procedures and characterization data
for all new compounds. The class will automatically add a sentence pointing to the infor-
mation on-line:

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