1

Understanding the physical

response of perovskite solar cells
by frequency domain methods

Juan Bisquert
Institute of Advanced Materials (INAM)
Universitat Jaume I
12006 Castelló
Spain

2020
Hybrid halide perovskites solar cell
A = MA+, Cs+, FA+, EA+
ABX3 B = Pb2+, Sn2+,
X = l-, CI-, Br -,

3
Park et al. Chem. Rev. 2020, 120, 15, 7867-7918

4
Mixed ionic-electronic conduction
electronic transport Ion transport

D
d 
d2
cm2 s-1

Q. Zhao et al. The Journal of Physical Chemistry Letters 2017, 8,

4122−4128.
Senocrate, Maier et al. Nat. Mater. 2018 17, 445–449. 5
 Evidence for ionic drift

• The drift of ionic vacancies under applied

electrical field (1 V)
• The advance of ions quenched luminescence
• The original state is recovered without
degradation

Li, C.; Guerrero, A.; J.; Huettner, S. Bisquert, J.; Nature Communications 9, 5113, (2018)
Unravelling the role of vacancies in lead halide perovskite through electrical switching of photoluminescence 6
 Perovskite is a solid electrolyte
polarization at electrodes
+
+
+
Formation of polarization and
space-charge: electrostatics

• The capacitance probes the extent of

polarization

• The interface capacitance is limited by the

Helmholtz capacitance
• In the order of 10 μF/cm2.

Kim, H.S., Guerrero, A., Bisquert, J., Park, N.G. et al.,. Control of I–V hysteresis in CH 3NH3PbI3 perovskite solar cell,  The
7
Journal of Physical Chemistry Letters, 6, 4633-4639 (2015).
 Capacitance in the dark:
interface and bulk polarization

• The bulk contribution indicates

dielectric relaxation at high
frequency

• The low frequency large contribution

indicates electrode polarization

Bulk
Dielectric relaxation
Interface
G. Garcia-
Belmonte
Ionic double layer
INAM-UJI
Castelló

Almora, O.; Zarazua, I.; Mas-Marza, E.; Mora-Sero, I.; Bisquert, J.; Garcia-Belmonte, G. JPCL 2015, 1645-1652.
Guerrero, A.; et al The Journal of Physical Chemistry C 2016, 120, 8023-8032. 8
 Surface polarization under light and voltage

+
+
+
Formation of polarization and
space-charge: electrostatics

R Gottesman, P Lopez-Varo, L Gouda, JA Jimenez-Tejada, J Hu,

The Journal of Physical Chemistry C, 2018, Bisquert, Zaban, Chem 1 (2016), 776-789
Garcia-Rosell, M.; Bou, A.; Jiménez-Tejada, J.Antonio; Bisquert, J.; Lopez-Varo, P.

9
 Surface polarization under light and voltage

+
+
+
Formation of polarization and
space-charge: electrostatics

The amount of charge is sensitive to

nature of the interface
• Fundamental connection to nature
of hysteresis

Kim, H.S., Guerrero, A., Bisquert, J., Park, N.G. et al.,. Control of I–V hysteresis in CH 3NH3PbI3 perovskite solar cell,  The
10
Journal of Physical Chemistry Letters, 6, 4633-4639 (2015).
 Kinetic low frequency phenomena in perovskite
Evac

+
+
+
Ion transport • Formation of polarization and
space-charge: electrostatics
• Fast process, no slow delay

+
+
+
• Specific ion binding and/or weak reaction
• Affects electron transfer and recombination
• Slow process: relates to hysteresis τ =1 −10 s

H. Wang, Bisquert, J.; Guerrero, A., A. Bou, A Al-Mayouf, Energy Environ. Sci., 2019, 2054-2079 11
INTERPRETATION OF IMPEDANCE
SPECTROSCOPY
The impedance spectra can be described by an equivalent
circuit that indicates the physical resistances and capacitances
Impedance spectroscopy measures the relation of
current to voltage in ac perturbation, while scanning the
measuring frequency w

τ =𝑅
τ =𝑅1 𝐶1
1 𝐶1 𝜔=
1
𝜏

𝑅1
τ =𝑅1𝐶1

Bisquert, J.; Guerrero, A., Garcia-Belmonte in preparation 13

 Impedance spectroscopy model
• The basic equivalent circuit for
perovskite solar cells contains two
features and a series resistance

Guerrero, A., Bisquert, J.; Garcia-Belmonte in preparation 14

Voltage-independent behaviour for the slow time
constant.

A. R. Pascoe, N. W. Duffy, A.
D. Scully, F. Huang, Y.-B.
Cheng, J. Phys. Chem. C 2015,
119, 4444–4453.
I. Zarazua, G. Han, P. P. Boix, S. Mhaisalkar, F. Fabregat-Santiago, I.
Mora-Seró, J. Bisquert, G. Garcia-Belmonte, J. Phys. Chem. Lett.
2016, 7, 5105-5113. 15
Timescales of the kinetic phenomena in a
perovskite solar cell with contacts
Type Time
Electronic transport across
100 nm

Electronic
Recombination/extraction
Halide vacancy diffusion
over a distance 100 nm
The response of ions
accumulated at the perovskite
surface
Cation vacancy diffusion
over a distance 100 nm

Very slow transport: Abate et

al.
H. Wang, Bisquert, J.; Guerrero, A., A. Bou, A Al-Mayouf, Energy Environ. Sci., 2019, 2054-2079 16
Guerrero, A., Bisquert, J.; Garcia-Belmonte in preparation 17
3rd arc and negative capacitance

18
 Beneficial chemical reactivity effect: Current voltage
curve clearly Improves with cycling

• Large crystal MAPbBr cell

with direct Gold contact

• This is the opposite of usual

degradation of perovskite
solar cell under Voltage
cycling

C Aranda, Bisquert, J.; Guerrero, A., J. Chem. Phys. 151, 124201 (2019); 19
Ionic reactivity improves
charge transfer rate

• Analysis of capacitance vs frequency

• ionic double layer decoupled from chemical reactivity and

electronic accumulation at the contacts.

• Shows the effect of OMETAD and the formation of an oxidized

layer under V cycling

Double layer Oxidized contact

+
+
+

C Aranda, Bisquert, J.; Guerrero, A., J. Chem. Phys. 151, 124201 (2019); 20
LIGHT MODULATED FREQUENCY
TECHNIQUES
 IMPS (Intensity-modulated photocurrent spectroscopy)

Modulated photon flux

+ Modulated current
-

External DC voltage
Monochromatic (470 nm),
20 kHz- 10 mHz

IMPS transfer function

Q plane plot –
Real part of Q vs
imaginary part of Q

22
Sandheep
Ravishankar
23
 Frequency dependent EQEPV-DIFF

The low frequency value of

IMPS is the differential EQE

EQEPV-DIFF is a function of frequency

due to the slow response of PSCs

Ravishankar, S., Aranda, C., Boix, P.P., Anta, J.A., Bisquert, J. and Garcia-Belmonte, G., Effects of Frequency
Dependence of the External Quantum Efficiency of Perovskite Solar Cells. JPCLett 9. 399 (2018) 24
 IMPS:
Perovskite solar cell equivalent circuit

• LF capacitor causes response in lower quadrant

• LF resistor acts like a series resistor, lowers EQEPV-DIFF

Ravishankar, S., Aranda, C., Boix, P.P., Anta, J.A., Bisquert, J. and Garcia-Belmonte, G., Effects of Frequency Dependence of the
25
External Quantum Efficiency of Perovskite Solar Cells. J. Phys. Chem. Lett 9, 399 (2018)
IMPS equivalent circuit for perovskite solar cell

IMPS IS

Ravishankar, S., Aranda, C., Sanchez, S., Bisquert, J., Saliba, M. and Garcia-Belmonte, G., 2019. Perovskite Solar Cell Modeling
Using Light and Voltage Modulated Techniques. The Journal of Physical Chemistry C. 26
SPECTRAL CORRELATION OF
ELECTROOPTICAL FREQUENCY
TECHNIQUES
IS, IMPS and IMVS measurements on
carbon-based Perovskite Solar Cells

Three different thicknesses

• Cell 1: Regular Cell (1.5 μm)

• Cell 2: Double Thickness Cell (3 μm)

• Cell 3: Triple Thickness Cell (4.5 μm)

28
IS, IMPS and IMVS measurements on
carbon-based Perovskite Solar Cells
 Surface polarization model

Relaxation equation

dVs Vs  (V  Vbi )

dt  kin

Ghahremanirad, E.; Bou, A.; Olyaee, S.; Bisquert, J. , The Journal of Physical Chemistry
30
Letters, 2017, 8, 1402
31
Equivalent Circuit for IS with midfrequency
arcs and negative capacitances
Negative Capacitances
and Inductive Loops

Midfrequency arcs

32
Fitting of IS Data
PEROVSKITE MEMRISTOR
 Introduction to memristors
• A memristor is a device that has
different metastable states at a
voltage V
• It has a resistance that depends
on the history of the system
• The states can be switched by
applied voltage.
• It is simpler than a transistor in
that the control occurs by 2
contacts

artificial synapsis for neuromorphic computation

memory storage

35
Lead Halide Memristors
• 2D Perovskites forms memristor devices

• The device that has two metastable states well

defined that last long time

• There is a variety of material response depending

on layering and contacts

Solanki, A.; Guerrero, A.; Zhang, Q.; Bisquert, J.; Sum, T.C. J. Phys. Chem. Lett. 2020, 11, 463−470 36
 Interfacial resistance decrease orders of magnitude

• Current increases

ON
ON State
OFF

Solanki, A.; Guerrero, A.; Zhang, Q.; Bisquert, J.; Sum, T.C. J. Phys. Chem. Lett. 2020, 11, 463−470 37
Movement of ions modifies the the electronic
barrier at the interface, from very high to low
resistance
Capacitance increases,
indicating the change of the
interfacial layer

Ionic double layer AgI layer

+
+
+

Solanki, A.; Guerrero, A.; Zhang, Q.; Bisquert, J.; Sum, T.C. J. Phys. Chem. Lett. 2020, 11, 463−470 38
Abnormal decrease of the resistance in impedance spectra shows
intrinsic instability
• The system is not stable during impedance measurement
• There is an interaction of system evolution and frequency scan
• But no negative capacitance

ON
OFF

39
REMOVAL OF LOW FREQUENCY
INSTABILITIES
we identify that the low-frequency arc/tail is in certain cases
an artefact generated by time drift of the sample

Methods
• Kramers-Kronig transform
• time course interpolation
• a corrective Z-HIT algorithm

J. Phys. Chem. C. Removing Instability-Caused Low-Frequency Features in Small Perturbation Spectra of

Perovskite Solar Cells S. Ravishankar, M. Garcia-Batlle, J. Bisquert, G. Garcia-Belmonte, J. Odrobina, C.-A. Schiller 41
the low frequency loop almost vanishes if time drift effect is
suppressed while a small loop in the inverse direction comes up at
the LF end

J. Phys. Chem. C. Removing Instability-Caused Low-Frequency Features in Small Perturbation Spectra of

Perovskite Solar Cells S. Ravishankar, M. Garcia-Batlle, J. Bisquert, G. Garcia-Belmonte, J. Odrobina, C.-A. Schiller 42
 Acknowledgments

Juan Bisquert
Follow @physolcell

Antonio Guerrero
Germà Garcia-Belmonte
Sandheep Ravishankar
Agustin Bou

Visit www.nanoge.org
for videos on scientific publishing

43
Visit https://www.youtube.com/

44
 JPC Letters Editorial Team

Greg Scholes Juan Bisquert Maria Forsyth Benedetta Oleg V. Prezhdo

Senior Editor Mennucci Senior Editor Jin Z. Zhang
Editor in Chief Senior Editor
Deakin University Senior Editor University of Southern Senior Editor
Princeton Universitat Jaume I,
University of Pisa California UC Santa Cruz
University Spain

Kate Luckey Sai Konda William Aumiller

Coordinating Editor Senior Managing Editor Development Editor
Princeton Unviersity ACS Publications ACS Publications 45
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Thank you

48
LONG RANGE ION TRANSPORT
 Ionic and electronic transport
• Long range transport 300 mm

Planar film with

lateral symmetric
contacts

• Solar cell operation

300 nm
50
 Suppressing luminescence by ionic drift
• The drift of ionic vacancies under
applied electrical field (1 V)
• The advance of ions quenched
luminescence
• The original state is recovered without
degradation

Li, C.; Guerrero, A.; J.; Huettner, S. Bisquert, J.; Nature Communications 9, 5113, (2018)
Unravelling the role of vacancies in lead halide perovskite through electrical switching of photoluminescence 51
 Ionic advance suppresses EL
• The dominant current is electronic
current, since electronic conductivity is
large

• The ions generate defects that cause

non-radiative recombination

direct evidence for massive ions

displacement
Li, C.; Guerrero, A.; J.; Huettner, S. Bisquert, J.; Nature Communications 9, 5113, (2018)
Unravelling the role of vacancies in lead halide perovskite through electrical switching of photoluminescence 52
 Suppressing PL by ionic drift
7. The formation of a dark region:
Local solid state reaction induces nonradiative
recombination center

Li, C.; Guerrero, A.; J.; Huettner, S. Bisquert, J.; Nature Communications 2018
53
 Suppressing PL by ionic drift
5. Calculation of the velocity of the front
12

( )
−1 /2
2𝛾
𝑗= 1+ 𝑣0 𝑡 𝑗0 10
𝑑 8

1/I (10 A )
-2
1 1

10
2
= 2
+ 𝑎𝑡 6
𝑗 𝑗0

2
4
2 𝛾 𝑣0
𝑎= 2
2
𝑑 𝑗0
0
0 10 20 30 40
Time (s)

6. Calculation of diffusion coefficient of ionic

defects in MAPI
DVI  2.4 108 cm 2 s -1

Li, C.; Guerrero, A.; J.; Huettner, S. Bisquert, J.; Nature Communications 2018
54
 Measurement of ionic diffusion coef.
Reduce the electronic current by using very low doping concentration perovskites: Use
monocrystals with low defect concentration

A. Guerrero
INAM-UJI Castelló
D
d 
d2
Equilibration time in 100 nm layer

cm2 s-1
Osman Bakr
KAUST

ACS Energy Letters, 2018, 3, 1477−1481.

Peng, W.; Aranda, C.; Bakr, O.M.; Garcia-Belmonte, G.; Bisquert, J.; Guerrero, A. 55
SURFACE POLARIZATION AT THE
CONTACTS
 Polarization at electrodes
+
+
+
Formation of polarization and
space-charge: electrostatics

Asymmetric charge distribution • The interface capacitance is

limited by the Helmholtz
capacitance

• In the order of 10 μF/cm2.

Almora, O.; Zarazua, I.; Mas-Marza, E.; Mora-Sero, I.; Bisquert, J.; Garcia-Belmonte, G. JPCL 2015, 1645-1652.
Bergmann, V.W., Weber, S.A. et al, ACS Applied Materials & Interfaces 2016, 8 (30), 19402-19409. 57