Effect of crystal symmetry of lead halide perovskites on the optical orientation of

excitons
Nataliia E. Kopteva1 , Dmitri R. Yakovlev1 , Eyüp Yalcin1 , Ina V. Kalitukha1 , Ilya A. Akimov1 , Mikhail O. Nestoklon1 ,
Bekir Türedi2,3 , Oleh Hordiichuk2,3 , Dmitry N. Dirin2,3 , Maksym V. Kovalenko2,3 , and Manfred Bayer1
1
Experimentelle Physik 2, Technische Universität Dortmund, 44227 Dortmund, Germany
2
Laboratory of Inorganic Chemistry, Department of Chemistry and
Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland and
3
Laboratory for Thin Films and Photovoltaics, Empa-Swiss Federal Laboratories
for Materials Science and Technology, CH-8600 Dübendorf, Switzerland
(Dated: November 7, 2024)
arXiv:2411.03764v1 [cond-mat.mtrl-sci] 6 Nov 2024

The great variety of lead halide perovskite semiconductors represents an outstanding platform
for studying crystal symmetry effects on the spin-dependent properties. Access to them is granted
through optical orientation of exciton and carrier spins by circularly polarized photons. Here,
the exciton spin polarization is investigated at 1.6 K cryogenic temperature in four lead halide
perovskite crystals with different symmetries: (almost) cubic in FA0.9 Cs0.1 PbI2.8 Br0.2 and FAPbBr3 ,
and orthorhombic in MAPbI3 and CsPbBr3 . Giant optical orientation of 85% is found for the
excitons in FA0.9 Cs0.1 PbI2.8 Br0.2 , MAPbI3 , and CsPbBr3 , while it amounts to 20% in FAPbBr3 .
For all studied crystals, the optical orientation is robust to detuning of the laser photon energy
from the exciton resonance, remaining constant for high energy detunings up to 0.3 eV, above
which it continuously decreases to zero for detunings exceeding 1 eV. No acceleration of the spin
relaxation for excitons with large kinetic energy is found in the cubic and orthorhombic crystals.
This evidences the absence of the Dyakonov-Perel spin relaxation mechanism, which is based on
the Rashba-Dresselhaus splitting of spin states at finite k-vectors. This indicates that the spatial
inversion symmetry is maintained in perovskite crystals, independent of the cubic or orthorhombic
phase.

Keywords tation11,12 , spin-flip Raman scattering13 , etc. The spin

dynamics at cryogenic temperatures extend to nanosec-
Lead halide perovskites, spintronics, excitons, optical onds for spin dephasing14 and to submilliseconds for lon-
spin orientation, time-resolved photoluminescence. gitudinal spin relaxation15 . The hyperfine interaction of
excitons and carriers with the nuclear spin system is es-
sential for the spin dynamics and relaxation9,14,16 , and
limits the spin relaxation time in weak magnetic fields.
I. INTRODUCTION
As shown recently, the giant optical orientation of exci-
ton spins in a FA0.9 Cs0.1 PbI2.8 Br0.2 crystal reaches 85%8 ,
The interest in studies of the optical properties of lead- close to the ultimate limit of 100%. This value is robust
halide perovskites is steadily growing due to their out- against detuning of the laser photon energy from the exci-
standing photovoltaic1 and optoelectronic properties2,3 . ton resonance up to 0.3 eV, providing strong experimen-
Their flexible chemical composition APbX3 , where the tal evidence that the Dyakonov-Perel spin relaxation is
cation A can be cesium (Cs+ ), methylammonium (MA+ ), absent and, therefore, the spin splitting in the conduction
formamidinium (FA+ ), and the anion X can be I− , and valence bands caused by the spin-orbit interaction is
Br− , Cl− , provides tunability of the band gap from zero in this particular crystal.
the infrared to the ultraviolet spectral range as well as
temperature-dependent crystal symmetries4 . The struc- In the lead halide perovskites, the spin-orbit coupling
tural phase transition from cubic symmetry at high tem- (SOC) is large due to the heavy lead ions, which is
peratures to orthorhombic one at cryogenic temperatures an essential prerequisite for the spin-dependent effects,
represents an excellent test bed for studying symmetry emerging from the Rashba and Dresselhaus spin split-
effects on spin-dependent properties which are impor- tings of the electron and hole bands at finite wave vec-
tant for applications in spintronics3,5–7 . In turn, the spin tors17 . The absence of spatial inversion symmetry is an-
physics sheds light on details of the crystal symmetry, as other key prerequisite for the SOC-induced effects. A
spin polarization and spin dynamics are highly suscepti- comprehensive review of the Rashba and Dresselhaus
ble to it. effects in the perovskite semiconductors, including po-
Many spin-related phenomena were explored in per- tential origins of inversion symmetry breaking, and ex-
ovskite bulk, two-dimensional, and nanocrystal struc- perimental approaches for detecting these effects can
tures. The exciton and carrier spins can be optically be found in Refs.18,19 . Theoretical predictions suggest
oriented by circularly polarized light8–10 , which is ex- strong Rashba-Dresselhaus splittings, but the mecha-
ploited in experimental techniques measuring photolu- nisms for symmetry breaking are still under debate. The
minescence polarization, time-resolved Faraday/Kerr ro- lead halide perovskites inherently have inversion sym-
 2

metry in their cubic crystal phase, and even when they II. RESULTS AND DISCUSSION
transition to the tetragonal or orthorhombic phases, this
inversion symmetry remains. The inversion symmetry Here, we examine four lead halide perovskite crystals
can be broken at the crystal surface20 , at boundaries be- with band gap energies (Eg ) in the visible spectral range
tween grains, and by application of external electric or of 1.5−2.4 eV and with different symmetries at cryogenic
strain field18,21 . For single crystals, the possible exis- temperatures, namely FA0.9 Cs0.1 PbI2.8 Br0.2 , FAPbBr3 ,
tence of ferroelectric phases has been suggested as static MAPbI3 , and CsPbBr3 .
mechanism for Rashba-Dresselhaus splittings22,23 . For
hybrid organic-inorganic perovskites, the orientation of
the organic cations (MA+ , FA+ ) and their dynamics may A. Optical properties
provide static or dynamic Rashba-Dresselhaus effects24 ,
which are not expected for the fully-inorganic perovskites The optical properties of the studied crystals at T =
with Cs+ cations. However, even for the fully inorganic 1.6 K cryogenic temperature are collected in Figure 1.
CsPbI3 crystals, vibrational instabilities were predicted The spectra of reflectivity (R) or photoluminescence ex-
to give rise to dynamic distortions of the lattice25 . Given citation (the latter for FA0.9 Cs0.1 PbI2.8 Br0.2 ) each show
this unclear situation, unique experimental evidences are a pronounced exciton resonance, marked by an arrow
required to establish which mechanisms are relevant for and labelled with EX . Time-integrated photolumines-
which materials and for what experimental conditions. cence (PL) spectra shown by the blue lines demonstrate
The experiments available so far are insufficient for a Stokes shift of about 6 − 10 meV from the energy of the
a comprehensive understanding of the bulk Rashba- exciton resonance. The emission is contributed by bound
Dresselhaus effects. A large Rashba splitting was or localized excitons and by recombination of electrons
observed in angle-resolved photoemission spectroscopy and holes separated spatially8,9,32,33 .
(ARPES) on a MAPbBr3 single crystal26 and by two- We are interested in excitons with a short recombina-
photon absorption spectroscopy27 . However, the ARPES tion time. Their emission can be isolated spectrally and
technique is sensitive only to the symmetry breaking temporally by measuring time-resolved PL using a streak
at the surface. The presence of the surface Rashba ef- camera, as shown in Figure 2(a) for MAPbI3 . Right after
fect on a MAPbBr3 single crystal was confirmed by the the excitation pulse action, the emission has its spectral
circular photogalvanic effect28 . Later, the absence of maximum at EX = 1.636 eV, as demonstrated in Fig-
the static Rashba-Dresselhaus splitting was evidenced by ure 1(b) by the red line. The exciton dynamics spec-
ARPES experiments on MAPbBr3 and CsPbBr3 crys- trally integrated in the range of 1.635 − 1.645 eV are
tals29 , and by second harmonic generation experiments shown in Figure 2(b). The dynamics can be fitted with
on MAPbBr3 crystals30 . In MAPbI3 crystals, the dy- a three-exponential decay function. We assign the two
namical Rashba effect caused by thermally induced struc- short decay times of τR1 = 15 ps and τR2 = 80 ps to the
tural fluctuations that break the inversion symmetry was exciton recombination. The long-lived component with
evidenced by measuring the circular photogalvanic ef- τR3 = 810 ps is provided by recombination of spatially
fect31 . The resulting spin splitting is the key basic as- separated electrons and holes. It is a common feature for
pect in the studied effects. Therefore, spin physics tech- bulk perovskites that the recombination of electron-hole
niques, which allow one to study spin splittings and spin pairs and of excitons is spectrally overlapping9,11,13,14 .
dynamics can greatly contribute to understanding this Ref.9 shows how these contributions can be separated by
still unresolved problem. employing the Hanle and polarization recovery effects in
In the present paper, we study the spin orienta- a magnetic field.
tion and relaxation of excitons to clarify the effect of Spectrally, the exciton emission matches the resonance
the spin-orbit coupling and identify a possible break- in the PL excitation spectrum for FA0.9 Cs0.1 PbI2.8 Br0.2 ,
ing of the inversion symmetry in various perovskite and in the reflectivity spectra for MAPbI3 and FAPbBr3 .
single crystals. We chose four lead halide perovskite Its time-integrated contribution is considerably weaker
crystals, FA0.9 Cs0.1 PbI2.8 Br0.2 , FAPbBr3 , MAPbI3 , and than the one of the Stokes shifted PL, so that in the time-
CsPbBr3 m that can be distinguished by: (i) different integrated spectra (blue lines in Figure 1), the exciton
halogens (I and Br) determining the band gap energy, (ii) emission is not observed as separate line, but as high-
different cations (FA+ , MA+ , Cs+ ), (iii) hybrid organic- energy shoulder. In the CsPbBr3 crystal with a strong
inorganic and fully-inorganic perovskites, and (iv) differ- exciton-polariton effect34 , a separate emission line is seen
ent crystal symmetries at cryogenic temperatures ranging arising from the upper polariton branch at 2.3375 eV, see
from almost cubic to orthorhombic. This crystal selection the red line in Figure 1(d).
allows us to investigate the influence of these features on
the optical orientation of exciton spins and on the exci-
ton spin relaxation. In turn, we get information about B. Optical orientation of exciton spins
the crystal symmetries, namely that the spatial inversion
symmetry inherent to the cubic perovskite crystals is not The optical orientation of exciton spins induced by cir-
broken in the orthorhombic crystals. cularly polarized laser excitation is illustrated for the
 3

FIG 1. Optical properties of the studied lead halide perovskite crystals with various band gaps at 1.6 K temperature. The blue
lines show time-integrated photoluminescence spectra measured for pulsed excitation at Eexc = 3.06 eV using the laser power
density of 5 mW/cm2 . The green lines show the PL excitation spectrum for FA0.9 Cs0.1 PbI2.8 Br0.2 , but reflectivity spectra for
the other samples. EX marks the exciton resonance. PL spectra right after the excitation pulse t = 0 ps are depicted by the
red lines. Laser excitation energy is Eexc = 1.669 eV for FA0.9 Cs0.1 PbI2.8 Br0.2 , 1.771 eV for MAPbI3 , 2.296 eV for FAPbBr3 ,
and 2.385 eV for CsPbBr3 .

FIG 2. Recombination dynamics for the MAPbI3 crystal at T = 1.6 K. (a) Contour plot of time-resolved photoluminescence
excited with 200 fs laser pulses at the laser photon energy of 1.771 eV. (b) Recombination dynamics integrated over the
δX = 1.635 − 1.645 eV spectral range around the exciton line maximum at EX = 1.636 eV. The green line is three-exponential
fit with decay times: τR1 = 15 ps, τR2 = 80 ps, and τR3 = 810 ps.

MAPbI3 example. Note that the MAPbI3 crystal has Here I ++ and I +− are the intensities of the σ + and σ −
orthorhombic symmetry at T = 1.6 K, which is well doc- polarized emission measured for σ + polarized excitation.
umented by its spin-dependent properties, including the The spectral dependence of Poo calculated by Eq. (1) is
strong anisotropy of the Landè g-factors of electron and presented in Figure 3(b). The maximal optical orienta-
hole13,35 . tion degree of 0.85 (or 85%) is observed at the high energy
Figure 3(a) shows the σ + and σ − circularly polarized flank of the exciton at 1.640 eV. Note that we reported re-
PL spectra right after σ + polarized excitation pulse ac- cently the same giant optical orientation of excitons for
tion (t = 0 ps). At the exciton energy, the σ + polarized FA0.9 Cs0.1 PbI2.8 Br0.2 crystals8 with almost cubic crys-
emission is considerably stronger than the σ − polarized tal symmetry at cryogenic temperatures, as confirmed
one, evidencing a large degree of optical orientation. The by isotropic carrier g-factors13,14 .
latter we define as:
The dynamics of the σ + and σ − circularly polarized
I++
−I +− exciton emission after the σ + polarized pulse are shown
Poo = ++
. (1) in Figure 3(c). The σ + polarized dynamics have a larger
I + I +−
 4

amplitude than in the opposite helicity, evidencing the ness against detuning of the excitation energy from the
large optical orientation degree. The dynamics of Poo (t) exciton resonance8 . This gives strong experimental evi-
are plotted in Figure 3(d). The maximal optical orien- dence that the spin splitting of the conduction and va-
tation degree of 0.85 is observed right after the pulse lence bands at finite wave vectors, which might be pro-
action. The optical orientation decreases with an initial vided by the Rashba and Dresselhaus effects, are absent
decay time of about 20 ps, saturating at about 0.45 for in materials with almost cubic crystal symmetry. There-
delays exceeding 200 ps, where excitons have already re- fore, it evidences that the lattice has inversion symmetry,
combined. This behavior is similar to the recently re- as expected for the crystal structure of cubic perovskites.
ported optical orientation for FA0.9 Cs0.1 PbI2.8 Br0.2 in This raises immediately the question whether the reduc-
Ref.8 , where it is shown that the decrease of Poo is tion of crystal symmetry to orthorhombic induces mech-
not related to exciton spin relaxation, but is determined anisms that break the inversion symmetry. To answer,
by exciton recombination. In this case, two recombi- MAPbI3 is the optimal material as its band gap is close
nation processes coexist at the same energy: fast exci- to that of FA0.9 Cs0.1 PbI2.8 Br0.2 , since the gap is con-
ton recombination and slower recombination of spatially trolled by the iodine anions, but the crystal symmetry
separated electrons and holes. The exciton spin relax- is reduced from cubic to orthorhombic below the phase
ation time strongly exceeds its recombination time (in transition temperature of 160◦ C.
FA0.9 Cs0.1 PbI2.8 Br0.2 by a factor of 5). The observed In Figure 4(a) the dependence of the exciton opti-
decrease of Poo reflects the fact that all highly-polarized cal orientation degree on the excitation energy detuned
excitons have recombined, and Poo at longer delays is to higher values relative to the exciton resonance is
contributed by the optical orientation of carriers with a shown for the MAPbI3 crystal by the blue triangles.
smaller degree of Poo 9 . Poo starts at 0.85 for small excitation energies relative
to EX and decreases weakly up to about 0.3 eV detun-
ing. The decrease becomes prominent for larger detun-
ings and Poo reaches zero for a detuning of about 1.4 eV.
This behavior is similar to the findings for almost cubic
FA0.9 Cs0.1 PbI2.8 Br0.2 crystals, shown here by the red cir-
cles. As the band gaps of these materials differ by about
0.1 eV, we plot for better comparison the data in Fig-
ure 5(a) as function of the detuning energy from the
exciton resonance (Eexc − EX ), so that EX = 0. The
dependences for the two materials coincide remarkably
well with each other. From these data, we conclude that
the reduction of crystal symmetry from almost cubic to
orthorhombic does not result in activation of any addi-
tional spin relaxation mechanisms. The main candidate
would be the Dyakonov-Perel mechanism which should
become efficient due to a spin splitting of the electron
and hole states at finite wave vectors in crystals without
inversion symmetry combined with a strong spin-orbit
interaction. Therefore, one can conclude that the spatial
FIG 3. Optical orientation of excitons in MAPbI3 crystal. inversion symmetry is maintained for the orthorhombic
(a) PL spectra right after σ + polarized excitation with 200 fs MAPbI3 crystal.
laser pulses (t = 0 ps, Eexc = 1.698 eV, excitation density
of 10 mW/cm2 ), measured in σ + (red line) and σ − (blue To collect comprehensive information on the whole
line) polarization. T = 1.6 K. (b) Spectral dependence of class of lead halide perovskite semiconductors, we exam-
the optical orientation degree calculated for the data in panel ine experimentally two more materials with bromine an-
(a). (c) PL dynamics measured in σ + (red line) and σ − (blue ions resulting in larger band gaps. These are the almost
line) polarization for σ + polarized excitation. The signal is cubic FAPbBr3 and the orthorhombic CsPbBr3 crystals.
detected in the spectral range of δX = 1.635 − 1.645 eV. (d) Their optical spectra are shown in Figures 1(c,d). In the
Dynamics of the optical orientation degree Poo (t). first material, the electron and hole g-factors are almost
isotropic36 , and in the second one the g-factors show a
pronounced anisotropy13 . The optical orientation of ex-
citons in these crystals measured at various excitation
energies is shown in Figure 4(b). For small detunings
C. Robustness of optical orientation against optical from EX , Poo (t = 0) reaches 0.85 in CsPbBr3 and 0.20 in
detuning FAPbBr3 . Despite the difference in the absolute values,
their dependence on excitation energy is very similar, as
The surprising peculiarity of optical orientation in can be better seen in Figure 5(a), where the data for
FA0.9 Cs0.1 PbI2.8 Br0.2 crystals is its outstanding robust- FAPbBr3 are multiplied by a factor of 4 to be normal-
 5

FIG 4. Optical orientation of excitons versus laser excitation energy. Dependence of Poo (t = 0) on Eexc for (a) MAPbI3 (blue)
and FA0.9 Cs0.1 PbI2.8 Br0.2 (red) as well as (b) FAPbBr3 (green) and CsPbBr3 (black). The excitation density is 10 mW/cm2
at T = 1.6 K. Arrows mark the exciton resonances (EX ) of corresponding materials.

ized to 0.85 value in CsPbBr3 . The basically identical be optically oriented with 100% efficiency. Also, due to
dependence on the detuning allows us to conclude that the presence of inversion symmetry of the crystal lat-
the difference in the optical orientation degree is pro- tice, spin splittings of the bands through the spin-orbit
vided by a more efficient spin relaxation of cold excitons interaction are absent, suppressing the spin relaxation
in FAPbBr3 . We suggest that the responsible mechanism by the Dyakonov-Perel mechanism. Instead, the spin
is provided by exciton interaction with the nuclear spin relaxation is governed by the rather inefficient Elliott-
fluctuations9,16 , which requires, however, further investi- Yafet mechanism and the electron-hole exchange inter-
gations beyond the scope of the present study. action in the exciton. These expectations are in agree-
In Figure 5(a) the exciton optical orientation in the ment with the observed high optical orientation degree of
four studied materials is compared. All of them show 0.85 measured for three of the studied materials. We can
a similar dependence on the excitation energy detuning, safely conclude that τs ≫ τR for the excitons in MAPbI3 ,
which evidences that the dependence is determined by FA0.9 Cs0.1 PbI2.8 Br0.2 , and CsPbBr3 .
the band structure of the lead halide perovskites around An in-depth theoretical analysis based on tight-binding
the band gap to energies 0.5 − 0.8 eV higher than the calculations of the spin initialization efficiency at large
conduction and valence band extrema. Here, we keep in detunings has been performed in Ref.8 . The line in Fig-
mind that the effective masses of electrons and holes in ure 5(a) shows the calculated dependence, which matches
the lead halide perovskites are about equal to each other. well the experimental data for all four materials. The
Note that the investigated excitation energy detuning is analysis shows that the decrease of optical orientation at
smaller than the spin-orbit-splitting ∆SO to the heavy- larger detunings originates from the deviation of the op-
and light-electron bands of about 1.2 − 1.5 eV and the tical helicity selection rules from the strict ones at the
energy gap at the M-point, which exceeds the band gap R-point. Also, additional depolarization comes from the
at the R-point by about 1.33 eV, see Figure 5(b). spin-flip scattering of excitons during the energy relax-
ation provided by the Elliott-Yafet mechanism.
It is well established that CsPbBr3 at low temperatures
D. Discussion has an orthorhombic crystal structure with space group
#62. This group has an inversion center, so that no spin
The optical orientation degree is determined by two splitting in the bands is expected. However, samples with
factors: (i) the efficiency of spin initialization induced organic cations (MA+ and FA+ ) may show a lower local
by circularly polarized photons for the interband opti- symmetry due to the oriented organic cations19 . Close
cal transition and (ii) the loss of spin polarization during similarities of spin properties found for Cs, MA, and FA-
the exciton lifetime τR . The latter is controlled by the based materials let us conclude that the latter effect does
factor τs /(τs + τR ) that reduces the initial optical orien- not contribute to spin dynamics.
tation, where τs is the exciton spin relaxation time. The We emphasize that the experimental technique used in
band structure of lead halide perovskites is favorable for our study delivers information about the exciton proper-
obtaining high optical orientation close to the ultimate ties inside a crystal and not at its surface, where excitons
limit of 100%8 . In the vicinity of the band gap, i.e., in are typically destroyed. Therefore, our experiments can-
the detuning range up to about 0.3 eV, the spins can not detect a possible breaking of the inversion symmetry
 6

FIG 5. (a) Optical orientation degree of excitons in various perovskite crystals as function of the optical detuning from
the exciton resonance. The data are taken from Figure 4 with the exciton energy set to zero. The values for FAPbBr3 are
multiplied by a factor of four for better comparison. The pink line is the theoretical dependence calculated with account for
the Elliott-Yafet spin relaxation due to interaction with longitudinal optical phonons, see Ref.8 . (b) Calculated band diagram
of bulk FA0.9 Cs0.1 PbI2.8 Br0.2 along the Γ → R → M → X path. The vertical lines indicate the transition energies at the R,
M , and X points from the valence band (VB) to the conduction band (CB1 ). The light- and heavy-electron bands CB2 are
shifted from CB1 by the spin-orbit splitting (∆SO ).

within the few monolayers close to the crystal surface, as for examining the effects associated with the crystal sym-
reported recently, e.g., for a MAPbBr3 single crystal by metry in perovskite nanostructures.
the circular photogalvanic effect28 .

IV. EXPERIMENTAL SECTION

III. CONCLUSION
Samples: We study single lead halide perovskite crys-
We have demonstrated that the exciton spins can tals with different band gaps. The crystals are grown out
be optically oriented in FA0.9 Cs0.1 PbI2.8 Br0.2 , MAPbI3 , of solution using the inverse temperature crystallization
CsPbBr3 , and FAPbBr3 crystals and in most of them a (ITC) technique40–42 . For the FA0.9 Cs0.1 PbI2.8 Br0.2 ,
very high degree of optical orientation of 85% is reached FAPbBr3 , and CsPbBr3 crystals studied here, details of
at cryogenic temperatures. For different perovskite com- the synthesis are given in Ref.13 . The MAPbI3 crystal
positions and symmetries, the optical orientation is ro- was synthesized from PbI2 and MAI perovskite precur-
bust against detuning of the laser excitation energy from sors between two polytetrafluoroethylene coated glasses,
the exciton resonance. We find that the exciton spin following Ref.43 . The sample has a square shape of
relaxation mechanisms are not influenced by the symme- 1 × 1 mm2 area in the (001) crystallographic plane with
try reduction from almost cubic to orthorhombic, evi- a thickness of 30 µm.
dencing that the spatial inversion symmetry inherent to The hybrid organic-inorganic compounds
cubic perovskite crystals is not broken for orthorhombic FA0.9 Cs0.1 PbI2.8 Br0.2 (Eg = 1.520 eV) and MAPbI3
crystals. (1.652 eV) have band gap energies close to the near-
In bulk perovskite crystals, the inversion symmetry infrared at T = 1.6 K temperature. Replacing the iodine
may be absent at their surface, and in polycrystalline halogen with bromine results in a blue shift of the band
films, it may get lost at the crystalline boundaries. Also, gap for FAPbBr3 (2.216 eV). To develop a complete
external factors, like axial strain and electric field, may picture, we also study the fully inorganic perovskite
break the inversion symmetry. The surface effect may CsPbBr3 (2.359 eV). The g-factor tensor of electrons and
become detrimental for perovskite nanocrystals and two- holes measured at the cryogenic temperatures is isotropic
dimensional materials, where a Rashba spin splitting has for FA0.9 Cs0.1 PbI2.8 Br0.2 and FAPbBr3 , reflecting their
been reported, based on experimental data27,37,38 and almost cubic crystal symmetry13 . Change of the cation
theoretical predictions38,39 . We are convinced that the from FA+ to MA+ and Cs+ leads to the symmetry
optical orientation technique is an extremely useful tool reduction, evidenced by a strong g-factor anisotropy of
 7

carriers13 . Dmitri R. Yakovlev – Experimentelle Physik

Optical measurements: For the low-temperature 2, Technische Universität Dortmund, 44227 Dort-
optical measurements, we use a liquid helium cryostat mund, Germany; orcid.org/0000-0001-7349-2745; Email:
with the temperature variable from 1.6 K up to 300 K. [email protected]
At T = 1.6 K, the sample is immersed in superfluid he-
lium.
Photoluminescence and reflectivity measure-
ments: The time-integrated photoluminescence (PL) Authors
and reflectivity spectra are measured with a 0.5 m spec-
trometer equipped with a charge-coupled-device (CCD) Eyüp Yalcin – Experimentelle Physik 2, Technische
camera. We use a halogen lamp as light source for the Universität Dortmund, 44227 Dortmund, Germany;
reflectivity measurements. orcid.org/0000-0003-2891-4173
Time-resolved photoluminescence: The
spectrally-resolved PL dynamics are measured us- Ina V. Kalitukha – Experimentelle Physik 2,
ing a spectrometer with a 300 grooves/mm diffraction Technische Universität Dortmund, 44227 Dortmund,
grating and a streak camera with 10 ps time resolution. Germany; orcid.org/0000-0003-2153-6667
Laser pulses with 200 fs duration and central photon
energies from 1.7 eV (730 nm) to 3.5 eV (350 nm) taken Ilya A. Akimov – Experimentelle Physik 2, Technis-
from a tunable Coherent Chameleon Discovery laser che Universität Dortmund, 44227 Dortmund, Germany;
(repetition rate of 80 MHz) with a second harmonic orcid.org/0000-0002-2035-2324
generation unit are used for PL excitation. To study the
effect of optical orientation, we use circular polarized Mikhail O. Nestoklon – Experimentelle Physik 2,
(σ + /σ − ) excitation light and subsequently analyze the Technische Universität Dortmund, 44227 Dortmund,
circular polarization of the emission. Germany; orcid.org/0000-0002-0454-342X

Bekir Türedi – Laboratory of Inorganic Chemistry,

Data Availability Statement Department of Chemistry and Applied Biosciences, ETH
Zürich, CH-8093 Zürich, Switzerland; Laboratory for
The data presented in this paper are available from the Thin Films and Photovoltaics, Empa-Swiss Federal Lab-
corresponding authors upon reasonable request. oratories for Materials Science and Technology, CH-8600
Dübendorf, Switzerland; orcid.org/0000-0003-2208-0737

Acknowledgements Oleh Hordiichuk – Laboratory of Inorganic Chem-

istry, Department of Chemistry and Applied Biosciences,
ETH Zürich, CH-8093 Zürich, Switzerland; Laboratory
The authors are thankful to Al. L. Efros and M. M.
for Thin Films and Photovoltaics, Empa-Swiss Federal
Glazov for fruitful discussions. We acknowledge the fi-
Laboratories for Materials Science and Technology,
nancial support by the Deutsche Forschungsgemeinschaft
CH-8600 Dübendorf, Switzerland; orcid.org/0000-0001-
via the SPP2196 Priority Program (projects YA65/28-1,
7679-4423
no. 527080192, and AK40/13-1, no. 506623857). I.V.K.
acknowledges the support of the Deutsche Forschungsge-
Dmitry N. Dirin – Laboratory of Inorganic Chem-
meinschaft (project KA 6253/1-1, no. 534406322). The
istry, Department of Chemistry and Applied Biosciences,
work at ETH Zürich (B.T., O.H., D.N.D., and M.V.K.)
ETH Zürich, CH-8093 Zürich, Switzerland; Laboratory
was financially supported by the Swiss National Science
for Thin Films and Photovoltaics, Empa-Swiss Federal
Foundation (grant agreement 200020E 217589) through
Laboratories for Materials Science and Technology,
the DFG-SNSF bilateral program and by ETH Zürich
CH-8600 Dübendorf, Switzerland; orcid.org/0000-0002-
through ETH+ Project SynMatLab.
5187-4555

Maksym V. Kovalenko – Laboratory of Inorganic

AUTHOR INFORMATION
Chemistry, Department of Chemistry and Applied
Biosciences, ETH Zürich, CH-8093 Zürich, Switzer-
Corresponding Authors land; Laboratory for Thin Films and Photovoltaics,
Empa-Swiss Federal Laboratories for Materials Science
Nataliia E. Kopteva – Experimentelle Physik and Technology, CH-8600 Dübendorf, Switzerland;
2, Technische Universität Dortmund, 44227 Dort- orcid.org/0000-0002-6396-8938
mund, Germany; orcid.org/0000-0003-0865-0393; Email:
[email protected] Manfred Bayer – Experimentelle Physik 2, Technis-
che Universität Dortmund, 44227 Dortmund, Germany;
 8

orcid.org/0000-0002-0893-5949

REFERENCES

1. A. K. Jena, A. Kulkarni, T. Miyasaka, Halide perovskite Zhang, D. Sun, Z.-G. Yu, V. Z. Vardeny, Y. S. Li, Spin-
photovoltaics: Background, status, and future prospects. polarized exciton quantum beating in hybrid organic–
Chem. Rev. 2019, 5, 3036–3103. inorganic perovskites. Nat. Phys. 2017, 13, 894.
2. Halide Perovskites for Photonics, eds. A. Vinattieri and 13. E. Kirstein, D. R. Yakovlev, M. M. Glazov, E. A. Zhukov,
G. Giorgi, (AIP Publishing, Melville, New York, 2021). D. Kudlacik, I. V. Kalitukha, V. F. Sapega, G. S. Dim-
3. Hybrid Organic Inorganic Perovskites: Physical Proper- itriev, M. A. Semina, M. O. Nestoklon, E. L. Ivchenko,
ties and Applications, eds. Z. V. Vardeny and M. C. N. E. Kopteva, D. N. Dirin, O. Nazarenko, M. V. Ko-
Beard, (World Scientific, 2022). valenko, A. Baumann, J. Höcker, V. Dyakonov, M. Bayer,
4. M. Simenas, A. Gagor, J. Banys, M. Maczka, Phase The Landé factors of electrons and holes in lead halide
transitions and dynamics in mixed three- and low- di- perovskites: universal dependence on the band gap. Nat.
mensional lead halide perovskites Chem. Rev. 2024, 124, Commun. 2022, 13, 3062.
2281. 14. E. Kirstein, D. R. Yakovlev, M. M. Glazov, E. Evers, E.
5. J. Wang, C. Zhang, H. Liu, R. McLaughlin, Y. Zhai, A. Zhukov, V. V. Belykh, N. E. Kopteva, D. Kudlacik,
S. R. Vardeny, X. Liu, S. McGill, D. Semenov, H. O. Nazarenko, D. N. Dirin, M. V. Kovalenko, M. Bayer,
Guo, R. Tsuchikawa, V. V. Deshpande, D. Sun, Z. V. Lead-dominated hyperfine interaction impacting the car-
Vardeny, Spin-optoelectronic devices based on hybrid rier spin dynamics in halide perovskites. Advanced Mate-
organic-inorganic trihalide perovskites. Nat. Commun. rials 2022, 34, 2105263.
2019, 10, 129. 15. V. V. Belykh, M. L. Skorikov, E. V. Kulebyakina, E.
6. W. Ning, J. Bao, Y. Puttisong, F. Moro, L. Kobera, S. V. Kolobkova, M. S. Kuznetsova, M. M. Glazov, D. R.
Shimono, L. Wang, F. Ji, M. Cuartero, S. Kawaguchi, S. Yakovlev, Submillisecond spin relaxation in CsPb(Cl,Br)3
Abbrent, H. Ishibashi, R. De Marco, I. A. Bouianova, G. perovskite nanocrystals in a glass matrix. Nano Lett.
A. Crespo, Y. Kubota, J. Brus, D. Y. Chung, L. Sun, W. 2022, 22, 4583–4588.
M. Chen, M. G. Kanatzidis, F. Gao, Magnetizing lead 16. E. Kirstein, D. S. Smirnov, E. A. Zhukov, D. R. Yakovlev,
free halide double perovskites. Science Advances 2020, 6, N. E. Kopteva, D. N. Dirin, O. Hordiichuk, M. V. Ko-
eabb5381. valenko, M. Bayer, The squeezed dark nuclear spin state
7. Y.-H. Kim, Y. Zhai, H. Lu, X. Pan, C. Xiao, E. A. in lead halide perovskites, Nat. Commun. 2023, 14, 6683.
Gaulding, S. P. Harvey, J. J. Berry, Z. V. Vardeny, J. M. 17. A. Manchon, H. C. Koo, J. Nitta, S. M. Frolov, R. A.
Luther, M. C. Beard, Chiral-induced spin selectivity en- Duine, New perspectives for Rashba spin–orbit coupling.
ables a room-temperature spin light-emitting diode. Sci- Nat. Mater. 2015, 14, 871.
ence 2021, 371, 1129. 18. M. Kepenekian, R. Robles, C. Katan, D. Sapori, L.
8. N. E. Kopteva, D. R. Yakovlev, E. Yalcin, I. A. Akimov, Pedesseau, J. Even, Rashba and Dresselhaus effects in
M. O. Nestoklon, M. M. Glazov, M. Kotur, D. Kudlacik, hybrid organic-inorganic perovskites: from basics to de-
E. A. Zhukov, E. Kirstein, O. Hordiichuk, D. N. Dirin, M. vices. ACS Nano 2015, 9, 11557.
V. Kovalenko, M. Bayer, Highly-polarized emission pro- 19. M. Kepenekian, J. Even, Rashba and Dresselhaus cou-
vided by giant optical orientation of exciton spins in lead plings in halide perovskites: accomplishments and op-
halide perovskite crystals. Adv. Sci. 2024, 11, 2403691. portunities for spintronics and spin-orbitronics. J. Phys.
9. D. Kudlacik, N. E. Kopteva, M. Kotur, D. R. Yakovlev, Chem. Lett. 2017, 8, 3362.
K. V. Kavokin, C. Harkort, M. Karzel, E. A. Zhukov, 20. E. Mosconi, T. Etienne, F. De Angelis, Rashba band split-
E. Evers, V. V. Belykh, M. Bayer, Optical spin orientation ting in organohalide lead perovskites: Bulk and surface
of localized electrons and holes interacting with nuclei in a effects. J. Phys. Chem. Lett. 2017, 8, 2247.
FA0.9 Cs0.1 PbI2.8 Br0.2 perovskite crystal. ACS Photonics 21. L. Leppert, S. E. Reyes-Lillo, J. B. Neaton, Electric field-
2024, 11, 2757. and strain-induced Rashba effect in hybrid halide per-
10. D. Giovanni, H. Ma, J. Chua, M. Grätzel, R. Ramesh, ovskites. J. Phys. Chem. Lett. 2016, 7, 3683.
S. Mhaisalkar, N. Mathews, T. Ch. Sum, Highly spin- 22. M. Kim, J. Im, A. J. Freeman, J. Ihm, H. Jin, Switchable
polarized carrier dynamics and ultralarge photoinduced S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide
magnetization in CH3 NH3 PbI3 perovskite thin films. perovskites. PNAS 2014, 111, 6900.
Nano Lett. 2015, 15, 1553-1558. 23. Zh.-G. Yu, Y. S. Li, Unraveling the spin relaxation mech-
11. V. V. Belykh, D. R. Yakovlev, M. M. Glazov, P. S. Grig- anism in hybrid organic–inorganic perovskites. J. Phys.
oryev, M. Hussain, J. Rautert, D. N. Dirin, M. V. Ko- Chem. C 2019, 123, 14701.
valenko, M. Bayer, Coherent spin dynamics of electrons 24. A. Marronnier, G. Roma, M. A. Carignano, Y. Bon-
and holes in CsPbBr3 perovskite crystals. Nat. Commun. nassieux, C. Katan, J. Even, E. Mosconi, F. De Angelis,
2019, 10, 673. Influence of disorder and anharmonic fluctuations on the
12. P. Odenthal, W. Talmadge, N. Gundlach, R. Wang, C. dynamical Rashba effect in purely inorganic lead-halide
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perovskites. J. Phys. Chem. C 2019, 123, 291. reflectivity in high magnetic fields and two-photon spec-
25. S. McKechnie, J. M. Frost, D. Pashov, P. Azarhoosh, A. troscopy. Phys. Stat. Sol. RRL 2024, 18, 2300407.
Walsh, M. van Schilfgaarde, Dynamic symmetry breaking 35. E. Kirstein, D. R. Yakovlev, E. A. Zhukov, J. Höcker,
and spin splitting in metal halide perovskites. Phys. Rev. V. Dyakonov, M. Bayer, Spin dynamics of electrons and
B 2018, 98, 085108. holes interacting with nuclei in MAPbI3 perovskite single
26. D. Niesner, M. Wilhelm, I. Levchuk, A. Osvet, S. crystals. ACS Photonics 2022, 9, 1375.
Shrestha, M. Batentschuk, C. Brabec, T. Fauster, Giant 36. E. Kirstein, E. A. Zhukov, D. R. Yakovlev, N. E. Kopteva,
Rashba splitting in CH3 NH3 PbBr3 organic-inorganic per- E. Yalcin, I. A. Akimov, O. Hordiichuk, D. N. Dirin, M. V.
ovskite. Phys. Rev. Lett. 2016, 117, 126401. Kovalenko, M. Bayer, Coherent carrier spin dynamics in
27. E. Lafalce, E. Amerling, Z.-G. Yu, P. C. Sercel, FAPbBr3 perovskite crystals. J. Phys. Chem. Lett. 2024,
L. Whittaker-Brooks, Z. V. Vardeny, Rashba split- 15, 2893-2903.
ting in organic–inorganic lead–halide perovskites revealed 37. Y. Zhai, S. Baniya, Ch. Zhang, J. Li, P. Haney,
through two-photon absorption spectroscopy. Nat. Com- Ch.-X. Sheng, E. Ehrenfreund, Z. V. Vardeny, Giant
mun. 2022, 13, 483. Rashba splitting in 2D organic-inorganic halide per-
28. Z. Huang, Sh. R. Vardeny, T. Wang, Z. Ahmad, A. ovskites measured by transient spectroscopies. Science
Chanana, E. Vetter, Sh. Yang, X. Liu, G. Galli, A. Amas- Advances 2017, 3, e1700704.
sian, Z. V. Vardeny, D. Sun, Observation of spatially re- 38. M. A. Becker, R. Vaxenburg, G. Nedelcu, P. C. Sercel,
solved Rashba states on the surface of CH3 NH3 PbBr3 sin- A. Shabaev, M. J. Mehl, J. G. Michopoulos, S. G. Lam-
gle crystals. Appl. Phys. Rev. 2021, 8, 031408. brakos, N. Bernstein, J. L. Lyons, Th. Stöferle, R. F.
29. M. Sajedi, M. Krivenkov, D. Marchenko, A. Varykhalov, Mahrt, M. V. Kovalenko, D. J. Norris, G. Rainó, Al. L.
J. Sánchez-Barriga, E. D. L. Rienks, O. Rader, Absence Efros, Bright triplet excitons in caesium lead halide per-
of a giant Rashba effect in the valence band of lead halide ovskites. Nature 2018, 553, 189-193.
perovskites. Phys. Rev. B 2020, 102, 081116. 39. P. C. Sercel, Al. L. Efros, Unique signatures of the
30. K. Frohna, T. Deshpande, J. Harter, W. Peng, B. A. Rashba effect in the magneto-optical properties of two-
Barker, J. B. Neaton, S. G. Louie, O. M. Bark, D. Hsieh, dimensional semiconductors. Phys. Rev. B 2023, 107,
M. Bernardi, Inversion symmetry and bulk Rashba effect 195436.
in methylammonium lead iodide perovskite single crys- 40. D. N. Dirin, I. Cherniukh, S. Yakunin, Y. Shynkarenko,
tals. Nat. Commun. 2018, 9, 1829. M. V. Kovalenko, Solution-grown CsPbBr3 perovskite sin-
31. D. Niesner, M. Hauck, Sh. Shrestha, I. Levchukc, G. J. gle crystals for photon detection. Chemistry of Materials
Matt, A. Osvet, M. Batentschuk, Ch. Brabec, H. B. We- 2016, 28, 8470–8474.
ber, Th. Fauster, Structural fluctuations cause spin-split 41. J. Höcker, F. Brust, M. Armer, V. Dyakonov, A
states in tetragonal (CH3 NH3 )PbI3 as evidenced by the temperature-reduced method for the rapid growth of hy-
circular photogalvanic effect. PNAS 2018, 115, 9509. brid perovskite single crystals with primary alcohols.
32. A. D. Wright, R. L. Milot, G. E. Eperon, H. J. Snaith, Cryst. Eng. Comm. 2021, 23, 2202–2207.
M.B Johnston, L.M. Herz, Band-tail recombination in hy- 42. O. Nazarenko, S. Yakunin, V. Morad, I. Cherniukh,
brid lead iodide perovskite. Adv. Funct. Mater. 2017, 27, M. V. Kovalenko, Single crystals of cesium formami-
1700860. dinium lead halide perovskites: solution growth and
33. D. W. deQuilettes, K. Frohna, D. Emin, T. Kirchartz, gamma dosimetry. NPG Asia Mater. 2017, 9, e373.
V. Bulovic, D. S. Ginger, S. D. Stranks, Charge-carrier 43. Ch. Yang, J. Yin, H. Li, Kh. Almasabi, L. Gutiérrez-
recombination in halide perovskites. Chem. Rev. 2019, Arzaluz, I. Gereige, J.-L. Brédas, O. M. Bakr, O. F.
119, 11007—11019. Mohammed, Engineering surface orientations for efficient
34. D. R. Yakovlev, S. A. Crooker, M. A. Semina, J. Rautert, and stable hybrid perovskite single-crystal solar cells.
J. Mund, D. N. Dirin, M. V. Kovalenko, M. Bayer, Ex- ACS Energy Lett. 2022, 7, 1544-1552.
citon–polaritons in CsPbBr3 crystals revealed by optical