Impedance spectroscopy and hysteresis effects of

halide perovskite solar cells and memristors

Juan Bisquert

22 05
Normal and inverted hysteresis

Mixed Halide Perovskite Solar Cells: Progress and Challenges

Mohammed S. G. Hamed &Genene Tessema Mola
2019 https://doi.org/10.1080/10408436.2018.1549976 2
To learn the amount of hysteresis you need to measure jV curves

Can we predict hysteresis just from the impedance spectra?

This will provide us insight about the causes

3
p–i–n tandems 27%

Aydin, E.; De Wolf, S. et al., Energy Environ. Sci. 2021, 14, 4377-4390. 4
IMPEDANCE SPECTROSCOPY OF
HALIDE PEROVSKITES
Solar cell operation

The energy delivered

We want to operate extracting

𝑃 𝑒𝑙= 𝑗𝑉 maximum power

The solar cell efficiency is a

product of:
-photocurrent
-fill factor
jxV -photovoltage

𝑗𝑚𝑝 𝑉 𝑚𝑝 𝑗 𝑝h ×𝐹𝐹 ×𝑉 𝑜𝑐
𝜂 𝑃𝐶𝐸= 𝑠𝑜𝑢𝑟𝑐𝑒 = 𝑠𝑜𝑢𝑟𝑐𝑒
Φ 𝐸 ,𝑡𝑜𝑡 Φ 𝐸 ,𝑡𝑜𝑡
6
 Impedance spectroscopy technique
Current, voltage and FF in
the solar cell depend on a
combination of processes
like charge separation,
Dual-source
recombination, contact
quality etc. co-deposition

Sequential - CVD

small perturbation:
linear response

Guerrero, A., Bisquert, J.; Garcia-Belmonte, Chemical Reviews 2021, 121, 14430–14484 7
Impedance Spectroscopy of Metal Halide Perovskite Solar Cells from the Perspective of Equivalent Circuits
Antonio Guerrero, Juan Bisquert* and Germà Garcia-Belmonte
Chem. Rev. 2021, 121, 23, 14430–1448

Significant change across

voltage stimulation

8
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

Guerrero, A., Bisquert, J.; Garcia-Belmonte, Chemical Reviews 2021, 121, 14430–14484 9
Perovskite is a mixed ionic-electronic conduction

electronic transport

Ion transport

Jon Mikel Azpiroz, Edoardo Mosconi, Juan Bisquert, Filippo De Angelis , Energy &
Environmental Science, 8, 2118-2127 (2015) 10
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. 11
Hybrid perovskite capacitance in the dark: electrode and bulk
polarization

In dark conditions

The bulk contribution indicates

dielectric relaxation at high
frequency

The low frequency large contribution

indicates electrode polarization
Interface Bulk
Ionic double layer Dielectric relaxation

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. 12
 Impedance spectroscopy model
•The basic equivalent circuit for perovskite solar
cells contains two features and a series resistance
Exponential changes under
external voltage

Guerrero, A., Bisquert, J.; Garcia-Belmonte, Chemical Reviews 2021, 121, 14430–14484 13
CHEMICAL INDUCTOR
The inductor element

𝑍 ( 𝑠 )= 𝐿𝑠
15
Bisquert, J.; Guerrero, A.
Chemical Inductor, J. Am. Chem. Soc. 2022, 144, 5996–6009.

16
FitzHugh-Nagumo model

Richard FitzHugh with analog computer at

NIH, ca. 1960
Memristive systems

Pershin, Y. V.; Di Ventra, M. Memory effects in complex materials and nanoscale systems,
Advances in Physics 2011, 60, 145-227. 18
 General dynamical model

(1)

(2)

19
Linear equations

(1)
(2)

The impedance takes the form

The circuit elements are defined as

;;

20
 Bisquert, J.; Guerrero, A.
Chemical Inductor, J. Am. Chem. Soc. 2022, 144, 5996–6009.

Fast-slow system forms a chemical inductor

Fast variable u, slow variable i

21
Nano Lett. 2006, 6, 640-650 22
 CdTe solar cell. Nano Lett. Halide perovskite single
OLED, Chem. Phys.
cristal. App. Phys. Lett. 2017,
Lett. 2006, 422, 184-191 2006, 6, 640-650
111, 163504
23
A. Bou, J. Bisquert. Impedance spectroscopy dynamics of biological neural elements: from memristors to neurons and
synapses, 24
J. Phys. Chem. B 2021, 125, 9934–9949.
HYSTERESIS IN HALIDE PEROVSKITE
DEVICES
Measure the jV curve

𝑉 ( 𝑡 )=𝑉 0 +𝑣 0 𝑡
voltage

time

Chen, B.; Yang, M.; Zheng, X.; Wu, C.; Li, W.; Yan, Y.; Bisquert, J.; Garcia-Belmonte, G.; Zhu, K.; Priya, S.
J. Phys. Chem. Lett. 2015, 6, 4693-4700. 26
 Voltage scan at rate s
𝑉 ( 𝑡 )=𝑉 0 +𝑣 0 𝑡
voltage

4
Increasing scan rate Forward capacitive current (s>0) increases
time 2

J (mA·cm )
-2
0
𝑑𝑄 𝑑𝑉 faster
𝑗𝐶 = =𝐶 -2
𝑑𝑡 𝑑𝑡
-4

𝑗𝐶 =𝑠𝐶
-0.9 -0.6 -0.3 0.0 0.3 0.6 0.9

Voltage (V)

Constant capacitance

Dark jV curve
27
 Capacitive hysteresis
correlates to capacitance in PSC with different
contacts
Capacitance
In dark in light

Kim, H.-S.; Jang, I.-H.; Ahn, N.; Choi, M.; Guerrero, A.; Bisquert, J.; Park, N.-G.
The Journal of Physical Chemistry Letters 2015, 6, 4633–4639. 28
Tuning the hysteresis by surface layers

Normal hysteresis Inverted hysteresis

a Hysteresis-normal b
0.06

Capacitive hysteresis: hysteresis index positive

Hysteresis effect index

0.04 Hysteresis-normal

0.02 Hysteresis-free
Inverted hysteresis: hysteresis index negative 0.00
Hysteresis-free

-0.02 Hysteresis-inverted

-0.04

-0.06 Hysteresis-inverted

4 3 2 1
c-TiO2 cycle

Rong Y., Juan Bisquert. Hongwei Han et al, Energy & Environmental Science 2017,10, 2383-2391. 29
Normal and inverted hysteresis

Mixed Halide Perovskite Solar Cells: Progress and Challenges, Mohammed S. G. Hamed & Genene Tessema Mola
2019 https://doi.org/10.1080/10408436.2018.1549976 30
Bisquert, J.; Guerrero, A.
Chemical Inductor, J. Am. Chem. Soc. 2022, 144, 5996–6009.

Inductive hysteresis: inverted

Forward capacitive current (s>0) decreases

faster

𝑗𝐶 =𝑠𝐶 negative capacitance

31
Transition from capacitor to inductor effect in MABrPb
perovskite solar cell

Juan Bisquert, Antonio Guerrero, and Cedric Gonzales

ACS Physical Chemistry Au 2021, 1, 25-44 32
Juan Bisquert, Antonio Guerrero, and Cedric Gonzales
ACS Physical Chemistry Au 2021, 1, 25-44 33
Capacitive and inductive hysteresis

Juan Bisquert, Antonio Guerrero, and Cedric Gonzales

ACS Physical Chemistry Au 2021, 1, 25-44 34
We can correlate hysteresis with impedance spectroscopy results

Juan Bisquert, Antonio Guerrero, and Cedric Gonzales

ACS Physical Chemistry Au 2021, 1, 25-44 35
From frequency domain to time domain

Juan Bisquert, Antonio Guerrero, and Cedric Gonzales

ACS Physical Chemistry Au 2021, 1, 25-44 36
HALIDE PEROVSKITE MEMRISTOR
TIME AND FREQUENCY DOMAIN
Memristors hysteresis

Chua, L. Memristor-The missing circuit element, IEEE Transactions on Circuit Theory 1971, 18, 507-519.
38
Halide perovskite memristor hysteresis
FTO/PEDOT:PSS/RP-
Perovskite/Ag/Au

Dr. Antonio Guerrero

INAM

A perovskite memristor
contains enormous
inverted hysteresis

Cedric Gonzales
INAM

C. Gonzales, A. Guerrero, J. Bisquert, Appl. Phys. Lett. 2021, 118, 073501

Ghahremanirad, E.; Bou, A.; Olyaee, S.; Bisquert, J. ,
The Journal of Physical Chemistry Letters, 2017, 8, 1402
Surface polarization model

Relaxation equation

𝑑𝑉 𝑠 𝑉 𝑠 −(𝑉 −𝑉 𝑏𝑖 )
=−
𝑑𝑡 𝜏 𝑘𝑖𝑛
40
Accumulation 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 41
 Berruet, M… Guerrero, A.; Bisquert, J.
Physical model for the current-voltage hysteresis and impedance of halide perovskite memristors,
ACS Energy Lett. 2022, 7, 1214–1222.

Memristor model for hysteresis

1
𝑓 (𝑢)= − ( 𝑢 − 𝑉 𝑇 ) /𝑉 𝑚
1+𝑒

Bisquert, J.; Guerrero, A. Chemical Inductor, J. Am. Chem. Soc. 2022, 10.1021/jacs.1022c00777.
42
We can describe several major techniques with just a few equations

More connected to different experiments tan drift-diffusion approach

It shows the way to a microscopic interpretation

43
Model for halide perovskite memristor

Berruet, M… Guerrero, A.; Bisquert, J. Physical model for the current-voltage hysteresis and impedance of
halide perovskite memristors, ACS Energy Lett. 2022, 7, 1214–1222.
Model for halide perovskite memristor
+

Berruet, M… Guerrero, A.; Bisquert, J. Physical model for the current-voltage hysteresis and impedance of
halide perovskite memristors, ACS Energy Lett. 2022, 7, 1214–1222.
46
Bisquert, J., Guerrero, A.
Dynamic Instability and Time Domain Response of a Model Halide Perovskite Memristor for Artificial Neurons
J. Phys. Chem. Lett. 2022, 13, 3789−3795

Time transient experiments

+
DETERMINE ELECTRON TRANSPORT
COEFFICIENT IN HALIDE PEROVSKITES
Transport in solar cells-diffusion model

49
 Transmission line for diffusion-recombination

( )
1/ 2
𝑅 𝑊 𝑅𝑘
𝑍=
1+ i 𝜔/ 𝜔𝑘
coth [ ( 𝜔𝑘 / 𝜔𝑑 ) ( 1+ i 𝜔/ 𝜔𝑘 )
1/ 2 1 /2
]

diffusion

50
Measurement of ionic diffusion in halide perovskites
Reduce the electronic current by using very low doping concentration perovskites: Use
monocrystals with low defect concentration

A. Guerrero
INAM-UJI Castelló
𝐷𝜇
𝜔 𝑑= 2
𝑑
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. 51
IMPS (Intensity-modulated photocurrent spectroscopy)

IMPS transfer function

Sandheep
Ravishankar

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. 52
Beyond Impedance Spectroscopy of Perovskite Solar Cells: Insights from the Spectral Correlation of
the Electrooptical Frequency Techniques
Agustín Bou, Adam Pockett… Juan Bisquert*
J. Phys. Chem. Lett. 2020, 11, 20, 8654–8659

Agustín Bou

Adam Pockett
Bertoluzzi, L.; Bisquert, J.,
Investigating the Consistency of Models for Water Splitting Systems by Light and Voltage Modulated Techniques.
J. Phys. Chem. Lett. 2017, 8, 172-180.

Spectral Correlation of IS, IMPS and IMVS

^ 1+ 𝑠 𝐶𝑎 𝑅𝑎 ^+ 𝑅𝑎 ^
𝐼= 𝑉 𝑞𝛷
𝑅𝑎 + 𝑅 𝑠 ( 1 + 𝑠 𝐶 𝑎 𝑅𝑎 ) 𝑅𝑎 + 𝑅 𝑠 ( 1 + 𝑠 𝐶 𝑎 𝑅𝑎 )
Luca Bertoluzzi
^ 1 ^ + 𝑄𝑞 𝛷
^
𝐼= 𝑉
𝑍

𝑄( 𝜔)=¿ ¿
54
Diffusion-recombination in IMPS
𝜕𝑛 𝜕2 𝑛 𝑛 −𝑛0 𝛼 (𝑥 − 𝑑 )
= 𝐷𝑛 − +𝛼𝛷 ( 𝑡 ) 𝑒
𝜕𝑡 𝜕𝑥 2
𝜏𝑛

Laurie Peter
Agustín Bou

55
A. Pockett, Michael Spence ,Suzanne K. Thomas, Dimitrios Raptis, Trystan Watson, Matthew J. Carnie
Beyond the First Quadrant: Origin of the High Frequency Intensity‐Modulated Photocurrent/Photovoltage Spectroscopy
Response of Perovskite Solar Cells
Solar RRL, 5, 2021 56
Extracting in Situ Charge Carrier Diffusion Parameters in Perovskite Solar Cells with Light Modulated Techniques
A Bou, H A̅boliņš, A Ashoka, H Cruanyes, A Guerrero, F Deschler,
ACS energy letters, 2021, 6, 2248-2255

Diffusion parameters from IMPS

a) collecting
contact
illum ination


photocurrent j
G(x)
electrons

holes

0 d
x

Felix Deschler
b) illum ination


photocurrent j
Au holes Perovskite
Al 2 O 3 electrons S nO 2

d 
0 x
57
From frequency domain to time transient methods for halide perovskite solar cells: The connections of IMPS, IMVS, TPC, and TPV
Juan Bisquert and Mathijs Janssen
J. Phys. Chem. Lett. 2021, 12, 7964–7971

From frequency to time domain

Mathijs Janssen

58
Limited information of impedance spectroscopy about electronic diffusion transport: The case of perovskite solar cells
A Bou, A Pockett, H Cruanyes, D Raptis, T Watson, MJ Carnie, J Bisquert
APL Materials 2022, 10, 051104

Limitations of difusion impedance

Agustín Bou

𝑄 ( 𝜔 )=¿ ¿

59
 Diffusion in frequency domain
𝑭 (𝝎)
𝑄 ( 𝜔 )=
IMPS
[( ) ]
1/2
𝑝
cosh
𝜔𝑑

𝑭 (𝝎 )
𝑊 ( 𝜔 )= 𝑅 𝑑
IMVS
( ) [( ) ]
1 /2 1/2
𝑝 𝑝
sinh
𝜔𝑑 𝜔𝑑

{ [( ) ] [ ( ) ]}
1/ 2 1 /2
( 𝑝 / 𝜔 𝑑 )1/ 2 𝑝 𝑝
1 − 𝑒− α 𝑑 𝑒 + − 1 sinh
𝜔𝛼 𝜔𝑑
𝑭 (𝝎 )=
[ 1 − 𝑝 / 𝜔𝛼 ]

Diffusion
impedance 𝑍 ( 𝜔 )= ¿ ¿
Mathijs Janssen
Locating the Frequency of Turnover in Thin-Film Diffusion Impedance
M Janssen, J Bisquert
60
The Journal of Physical Chemistry C 125 (28), 15737-15741
 Summary
•Regular hysteresis is capacitive
(Surface capacitance)

•Inductive hysteresis is inverted

(the chemical inductor)

•The equivalent circuit evolution

controls the dominant hysteresis

•We can measure reliably

difusión coefficient of electrons by
IMPS withour ionic interference

61
Acknowledgments
Juan Bisquert
Follow @physolcell

Antonio Guerrero
Agustín Bou
Cedric Gonzales

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