Optoelectronic techniques for diffusion and recombination

Juan Bisquert

22 11
INTRODUCTION
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 𝑝 h × 𝐹𝐹 ×𝑉 𝑜𝑐
𝜂 𝑃𝐶𝐸= 𝑠𝑜𝑢𝑟𝑐𝑒 = 𝑠𝑜𝑢𝑟𝑐𝑒
Φ 𝐸 ,𝑡𝑜𝑡 Φ 𝐸, 𝑡𝑜𝑡
3
 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 4
Limitations of impedance spectroscopy
The basic equivalent circuit for perovskite solar cells
contains two features and a series resistance

Guerrero, A., Bisquert, J.; Garcia-Belmonte, Chemical Reviews 2021, 121, 14430–14484 5
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. 6
Inductorhalide perovskite

Zohar, A.; Kedem, N.; Levine, I.; Zohar, D.; Vilan, A.; Ehre, D.; Hodes, G.; Cahen,, J. Phys. Chem. Lett. 2016, 7, 191-197.

Fabregat-Santiago, F. et al. ACS Energy Lett. 2017, 2, 2007-2013. 7

The chemical inductor is a general
denomination for a class of chemical and
material systems that provide the exact
electrical response of an inductor.

No electromagnetic effect or induction.

(1)

(2)

Bisquert, J.; Guerrero, A.

Chemical Inductor, J. Am. Chem. Soc. 2022, 144, 5996–6009. 8
The chemical inductor small signal ac response
Linearized equations,
change time derivative to
(1)
(2)

(
^𝐼 = 𝐶 𝑠+ 1 𝑓 + 1
𝑚
𝑓 𝑥 𝑔𝑢
)
𝑅 𝐼 𝑢 𝑅 𝐼 −𝑔 𝑥 +𝜏 𝑘 𝑠
^
𝑢
The circuit elements are defined as
Definition of impedance
^
𝑢 ;
𝑍=
^
𝐼
;
The impedance takes the form

9
 Chemical inductor

Short time response

f(u)/RI

𝑑𝑢
𝐼 =𝐶 𝑚
𝑑𝑡

u
10
Chemical inductor

Long time response

f(u)/RI

x(u)
𝑑𝑥
𝜏𝑘 = 𝑔( 𝑥 , 𝑢)
𝑑𝑡

u
11
Meaning of spectra of the chemical inductor

Short time/ high frequency

𝑅𝑏

12
Meaning of spectra
Long time/ low frequency

1 1
+
𝑅𝑏 𝑅𝑎 13
Ghahremanirad, E.; Bou, A.; Olyaee, S.; Bisquert, J. ,
The Journal of Physical Chemistry Letters, 2017, 8, 1402
Surface polarization model

Agustin Bou

𝑑𝑉 𝑠 𝑞 (𝑉 /𝛾 +𝑉 / 𝛽+𝑉 𝑏𝑖 / 𝛾 ) /𝑘 𝐵 𝑇
𝑗=𝐶 𝑎𝑐𝑐 + 𝑗𝑝 h − 𝑗𝑟𝑒𝑐 0 𝑒 𝑠

𝑑𝑡
𝑑𝑉 𝑠 𝑉 𝑠 −(𝑉 −𝑉 𝑏𝑖 )
=− Elnaz Ghahremanirad
𝑑𝑡 𝜏 𝑘𝑖𝑛
14
Ghahremanirad, E.; Bou, A.; Olyaee, S.; Bisquert, J. ,
The Journal of Physical Chemistry Letters, 2017, 8, 1402
Surface polarization model

Chemical inductor. The slow variable is the voltage

𝑑𝑉 𝑠 𝑉 𝑠 −(𝑉 −𝑉 𝑏𝑖 )
=−
𝑑𝑡 𝜏 𝑘𝑖𝑛

15
Enrique Hernández-Balaguera, Juan Bisquert
Negative Transient Spikes in Halide Perovskites, ACS Energy Lett. 2022, 2602-2610. 16
Capacitive and inductive hysteresis

Juan Bisquert, Antonio Guerrero, and Cedric Gonzales

ACS Physical Chemistry Au 2021, 1, 25-44 17
Transport in solar cells-diffusion model

F. Fabregat-Santiago, J. Bisquert, 2000-2010

18
 Transmission line for diffusion-recombination
( )
1/ 2
𝑅𝑊 𝑅𝑘
𝑍=
1+ i 𝜔/ 𝜔𝑘
coth [ ( 𝜔𝑘 / 𝜔𝑑 ) ( 1+ i 𝜔/ 𝜔𝑘 )
1/ 2 1 /2
]

diffusion Observed in dye-sensitized solar cellss

Not observed in halide perovskites

Wang, Q.; Ito, S.; Grätzel, M.; Fabregat-Santiago, F.; Mora-Seró, I.; Bisquert, J.; Bessho, T.; Imai, H. Characteristics of
high efficiency dye-sensitized solar cells, J. Phys. Chem. B 2006, 110, 19406-19411.
19
IMPS
Light stimulous
Voltage V V
Current I Impedance
Incoming light Fin spectroscopy
I Transfer function Z

Fin
IMPS
Transfer function Q
I
I(V) curve EQE I/F
Fin Fin
IMVS
V I I Transfer function W
V
21
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. 22
 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) 23
Laurie Peter

24
Juan Bisquert and Mathijs Janssen
J. Phys. Chem. Lett. 2021, 12, 33, 7964–7971 25
 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
26
External Quantum Efficiency of Perovskite Solar Cells. JPCLett 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. 27
ELECTRON DIFFUSION IN HALIDE PEROVSKITE
MEASURED BY INTENSITY MODULATED
PHOTOCURRENT SPECTROSCOPY (IMPS)
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

29
Diffusion-recombination in IMPS
𝜕 𝑛 𝑛 −𝑛0
2
𝜕𝑛 ( ) 𝛼 (𝑥 − 𝑑 )
= 𝐷𝑛 − +𝛼𝛷 𝑡 𝑒
𝜕𝑡 𝜕𝑥
2
𝜏𝑛

Laurie Peter

Adam Pockett

30
 Diffusion in IMPS
𝜕𝑛 𝜕2 𝑛 𝑛 −𝑛0 ( ) 𝛼 (𝑥 − 𝑑 )
=𝐷𝑛 − +𝛼𝛷 𝑡 𝑒
𝜕𝑡 𝜕 𝑥2 𝜏𝑛
Agustín Bou

[ 𝐿 )]
𝑧𝑑

𝑄 ( 𝜔 )=
1 −𝑒
−α 𝑑
( 𝐿𝑧 α − 1) sinh ( 𝑧𝑑
𝑒
𝐿𝑛
+
𝑛 𝑛

[ 𝐿α ] 𝐿)
( ) (
2
𝑧 𝑧𝑑
1− cosh
𝑛 𝑛

Three parameters:
Diffusion length (Ln)
Absorption coefficient (α)
Absorption layer thickness
(d)

A. Bou, H. A̅ boliņš, A. Ashoka, H. Cruanyes, A. Guerrero, F. Deschler, and J. Bisquert. Extracting in Situ Charge Carrier Diffusion
31
Parameters in Perovskite Solar Cells with Light Modulated Techniques. ACS Energy Lett. 2021, 6, 6, 2248–2255
Diffusion parameters from IMPS

𝐷𝑝 =0 . 029 0 . 034 cm 2 / s
𝐿𝑝=2 .2 2 . 6 μ m

A. Bou, H. A̅ boliņš, A. Ashoka, H. Cruanyes, A. Guerrero, F. Deschler, and J. Bisquert. Extracting in Situ Charge Carrier Diffusion
32
Parameters in Perovskite Solar Cells with Light Modulated Techniques. ACS Energy Lett. 2021, 6, 6, 2248–2255
Diffusion in QIBC device
1
𝑄 ( 𝜔 )= 𝑧𝑑

( )
𝐿𝑝 𝑧𝑑 1 𝐿
sinh +¿ 𝑒 ¿ 𝑝

𝛽 𝑧𝐷 𝑝 𝐿𝑝 𝛽𝛿

Felix Deschler

A. Bou, H. A̅ boliņš, A. Ashoka, H. Cruanyes, A. Guerrero, F. Deschler, and J. Bisquert. Extracting in Situ Charge Carrier Diffusion
33
Parameters in Perovskite Solar Cells with Light Modulated Techniques. ACS Energy Lett. 2021, 6, 6, 2248–2255
Diffusion in QIBC device
1
𝑄 ( 𝜔 )= 𝑧𝑑

( )
𝐿𝑝 𝑧𝑑 1 𝐿
sinh +¿ 𝑒 ¿ 𝑝

𝛽 𝑧𝐷 𝑝 𝐿𝑝 𝛽𝛿

𝐷𝑝 = 0 . 76 cm 2 / s𝐿 𝑝= 11μ m

A. Bou, H. A̅ boliņš, A. Ashoka, H. Cruanyes, A. Guerrero, F. Deschler, and J. Bisquert. Extracting in Situ Charge Carrier Diffusion
34
Parameters in Perovskite Solar Cells with Light Modulated Techniques. ACS Energy Lett. 2021, 6, 6, 2248–2255
The results of the measurements produce the
hole diffusion coefficient of
D = 0.029 cm /s and lifetime of τ = 16 μs
p 2 p

for one cell

and D = 0.76 cm /s and τ = 1.6 μs
p 2 p

for the other.

35
Frequency to time domain correlation

Pockett, A.; Spence, M.; Thomas, S. K.; Raptis, D.; Watson, T.; Carnie, M. J.; Beyond the First Quadrant. Sol. RRL 2021,5, 2100159 36
Laird et al. Small Methods 2022, 6, 2200493 37
Laser beam induced current (LBIC) mapping of perovskite solar cell

Laird et al. Small Methods 2022, 6, 2200493 38

39
40
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

41
CORRELATED FREQUENCY TECHNIQUES
IN SOLAR FUEL SYSTEMS
Investigating the Consistency of Models for Water Splitting Systems by Light and Voltage Modulated Techniques.
Bertoluzzi, L.; Bisquert, J.,
J. Phys. Chem. Lett. 2017, 8, 172-180.

Spectral Correlation of IS, IMPS and IMVS

Luca Bertoluzzi

𝑄(𝜔)=¿ ¿ 43
^ 1+ 𝑠 𝐶 𝑎 𝑅 𝑎 ^+ 𝑅𝑎 ^
𝐼= 𝑉 𝑞𝛷
𝑅𝑎 + 𝑅 𝑠 ( 1+ 𝑠 𝐶 𝑎 𝑅𝑎 ) 𝑅𝑎 + 𝑅 𝑠 ( 1+ 𝑠 𝐶 𝑎 𝑅𝑎 )

44
45
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
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

Electron difusión in halide perovskites is not observed in

impedance spectroscopy

Agustín Bou

𝑄 ( 𝜔 )=¿ ¿

It can be observed by IMPS

47
Correlation between the techniques
Here we show that the división of W and Q recovers the
impedance when series resistance is added

𝑊 ( 𝜔)
𝑄 (𝜔 )
𝑍 (𝜔 )

Bou, A.; Pockett, A.; Cruanyes, H.; Raptis, D.; Watson, T.; Carnie, M. J.; and Bisquert, J.; Limited information of impedance
spectroscopy about electronic diffusion transport: The case of perovskite solar cells. APL Mat. 2022, 10, 051104
iVO4 Photoelectrodes for water splitting

Francisco Fabregat-Santiago
INAM

Agustin O. Álvarez
INAM
𝑄(𝜔)=¿¿
New Views on Carrier Diffusion and Recombination by Combining Small Perturbation Techniques: Application to BiVO4 Photoelectrodes
Agustin O. Alvarez, Miguel García-Tecedor, Laura Montañés, Elena Mas-Marzá, Sixto Giménez, and Francisco Fabregat-Santiago
Solar RRL 2022 DOI: 10.1002/solr.202200826 49
BiVO4 Photoelectrodes for water splitting

New Views on Carrier Diffusion and Recombination by Combining Small Perturbation Techniques: Application to BiVO4 Photoelectrodes
Agustin O. Alvarez, Miguel García-Tecedor, Laura Montañés, Elena Mas-Marzá, Sixto Giménez, and Francisco Fabregat-Santiago
Solar RRL 2022 DOI: 10.1002/solr.202200826 50
LIGHT EMISSION FREQUENCY
SPECTROSCOPY
Light Emission Voltage Modulated Spectroscopy LEVS
Voltage V
Current I Fin
Incoming light Fin IMVS
Outgoing light Fout Transfer function W

V
F. Gao

V LEVS
Transfer function S

Fout
radiance (V)

V Fout
52
Dohyun Kwak, Matthias Paur, Kenji Watanabe, Takashi Taniguchi, and Thomas Mueller
Adv. Mater. Technol. 2022, 7, 2100915 53
 ^
𝑞𝛷 𝑜𝑢𝑡
V 𝑆=
LEVS ^
𝑉
Transfer function S

Fout ^
𝑞𝛷 𝑜𝑢𝑡
𝑃=
^
𝐼
I LEPS
Transfer function P 𝑃 = 𝑆𝑍
Fout

54
 Rafael S. Sánchez
Halide perovskite LED
ITO/PEDOT:PSS/Poly-TPD/
CsPbBr3 nanocrystal/POT2T/LiF/Al. Experiment

Oscilloscope
Input signal acquisition
(channel 2)
Output signal acquisition
(channel 1)
Wavefunction
generator

Collimating lenses CsPbBr3 LED

Silicon
amplified photodetector

Radiative recombination processes in halide perovskites observed by light emission voltage modulated spectroscopy
Rafael S. Sánchez, Alexis Villanueva-Antolí,Agustín Bou,Marta Ruiz-Murillo,Iván Mora-Seró,Juan Bisquert
Adv. Mat 2022 https://doi.org/10.1002/adma.202207993 55
 Rafael S. Sánchez

V LEVS
Transfer function S

Fout

Radiative recombination processes in halide perovskites observed by light emission voltage modulated spectroscopy
Rafael S. Sánchez, Alexis Villanueva-Antolí,Agustín Bou,Marta Ruiz-Murillo,Iván Mora-Seró,Juan Bisquert
Adv. Mat 2022 https://doi.org/10.1002/adma.202207993 56
57
Perovskite LEDS

Kovalemko et al. ACS Energy Lett. 2022, 7, 10, 3401-3414

58
Theory of LEVS

Radiative recombination processes in halide perovskites observed by light emission voltage modulated spectroscopy
Rafael S. Sánchez, Alexis Villanueva-Antolí,Agustín Bou,Marta Ruiz-Murillo,Iván Mora-Seró,Juan Bisquert
Adv. Mat 2022 https://doi.org/10.1002/adma.202207993 59
I LEPS
Transfer function P

Fout

60
Representation of the S function in the complex plane (arbitrary units) of the
LED6 at 4V DC ±20 mV AC, and that of a commercially available blue emitting
device (LED430L) at 3V DC ±20 mV AC.

61
 (a) (b) (c)
6 6 3
10 10 10
fh fd fa
Frequency (Hz)

Frequency (Hz)

Frequency (Hz)
105 105 102
LED1
LED 2
LED 3
104 LED 4 104 101
LED 5
LED 5+1KW
LED 6
LED 2 IS
103 103 100
3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 3.2 3.6 4.0 4.4 4.8 5.2 3.2 3.6 4.0 4.4 4.8 5.2
Potential (V) Potential (V) Potential (V)
62
63
Acknowledgments
Juan Bisquert
Follow @physolcell

Antonio Guerrero
Agustín Bou
Cedric Gonzales
Enrique Hernández-Balaguera

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