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M(III) Site-Driven Structural Engineering on Lead-Free Layered Double Perovskite Nanocrystals with Enhanced Photoelectrochemical Activity

Yukta LU orcid ; Rahman, Sunardi LU orcid ; Shi, Qi LU ; Al Said, Tarek ; Kasi Matta, Sri ; Hu, Tianyi LU ; Wang, Weimin LU orcid ; Opis-Basilio, Amanda ; Ray, Kallol and Dick, Kimberly A. LU , et al. (2025) In Small Structures 6(10).
Abstract
Over the past decade, organic–inorganic hybrid perovskites have
revolutionized next-generation semiconductors, driving unprecedented
advancements in cost-effective optoelectronics. While lead-based
perovskite semiconductors exhibit exceptional optoelectronic properties,
their inherent toxicity and vulnerability to environmental degradation
remain significant barriers to widespread commercialization.
Vacancy-ordered layered double perovskites (LDPs) offer a viable
alternative with direct bandgaps, reduced toxicity, superior stability,
and tunable properties, while their divalent and trivalent cation
integration enables precise control over electronic and photophysical
characteristics for... (More)
Over the past decade, organic–inorganic hybrid perovskites have
revolutionized next-generation semiconductors, driving unprecedented
advancements in cost-effective optoelectronics. While lead-based
perovskite semiconductors exhibit exceptional optoelectronic properties,
their inherent toxicity and vulnerability to environmental degradation
remain significant barriers to widespread commercialization.
Vacancy-ordered layered double perovskites (LDPs) offer a viable
alternative with direct bandgaps, reduced toxicity, superior stability,
and tunable properties, while their divalent and trivalent cation
integration enables precise control over electronic and photophysical
characteristics for efficient optoelectronics. Herein, the M(III) cation
site within the previously reported Cs4CoIn2Cl12 LDP system by substituting In3+ with Bi3+ and Sb3+ is systematically modified, achieving the first-ever colloidal synthesis of Cs4CoBi2Cl12 and Cs4CoSb2Cl12
nanocrystals (NCs). A detailed investigation of their optoelectronic
properties reveals significant structural distortions induced by
different M(III) cations. Stability assessments demonstrate that Cs4CoSb2Cl12
exhibits exceptional air and compositional stability, maintaining its
compositional integrity for over 100 days under ambient conditions.
Furthermore, the photoelectrochemical (PEC) performance of these NCs in
benzoquinone oxidation is explored, identifying Cs4CoBi2Cl12
as the most efficient candidate, with a stable photoresponse and
enhanced photocurrent generation. Transient absorption studies further
confirm that Cs4CoBi2Cl12
sustains the largest self-trapped exciton population and longest
half-lifetime, highlighting its potential for sustainable,
high-performance PEC devices. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Small Structures
volume
6
issue
10
article number
2500179
pages
12 pages
publisher
Wiley
external identifiers
  • scopus:105009233504
ISSN
2688-4062
DOI
10.1002/sstr.202500179
language
English
LU publication?
yes
id
0abad761-edbd-418d-b360-a72fdecfee85
date added to LUP
2025-12-02 10:00:30
date last changed
2025-12-04 13:28:39
@article{0abad761-edbd-418d-b360-a72fdecfee85,
  abstract     = {{Over the past decade, organic–inorganic hybrid perovskites have <br>
revolutionized next-generation semiconductors, driving unprecedented <br>
advancements in cost-effective optoelectronics. While lead-based <br>
perovskite semiconductors exhibit exceptional optoelectronic properties,<br>
 their inherent toxicity and vulnerability to environmental degradation <br>
remain significant barriers to widespread commercialization. <br>
Vacancy-ordered layered double perovskites (LDPs) offer a viable <br>
alternative with direct bandgaps, reduced toxicity, superior stability, <br>
and tunable properties, while their divalent and trivalent cation <br>
integration enables precise control over electronic and photophysical <br>
characteristics for efficient optoelectronics. Herein, the M(III) cation<br>
 site within the previously reported Cs<sub>4</sub>CoIn<sub>2</sub>Cl<sub>1</sub><sub>2</sub> LDP system by substituting In<sup>3</sup><sup>+</sup> with Bi<sup>3</sup><sup>+</sup> and Sb<sup>3</sup><sup>+</sup> is systematically modified, achieving the first-ever colloidal synthesis of Cs<sub>4</sub>CoBi<sub>2</sub>Cl<sub>1</sub><sub>2</sub> and Cs<sub>4</sub>CoSb<sub>2</sub>Cl<sub>1</sub><sub>2</sub><br>
 nanocrystals (NCs). A detailed investigation of their optoelectronic <br>
properties reveals significant structural distortions induced by <br>
different M(III) cations. Stability assessments demonstrate that Cs<sub>4</sub>CoSb<sub>2</sub>Cl<sub>1</sub><sub>2</sub><br>
 exhibits exceptional air and compositional stability, maintaining its <br>
compositional integrity for over 100 days under ambient conditions. <br>
Furthermore, the photoelectrochemical (PEC) performance of these NCs in <br>
benzoquinone oxidation is explored, identifying Cs<sub>4</sub>CoBi<sub>2</sub>Cl<sub>1</sub><sub>2</sub><br>
 as the most efficient candidate, with a stable photoresponse and <br>
enhanced photocurrent generation. Transient absorption studies further <br>
confirm that Cs<sub>4</sub>CoBi<sub>2</sub>Cl<sub>1</sub><sub>2</sub> <br>
sustains the largest self-trapped exciton population and longest <br>
half-lifetime, highlighting its potential for sustainable, <br>
high-performance PEC devices.}},
  author       = {{Yukta and Rahman, Sunardi and Shi, Qi and Al Said, Tarek and Kasi Matta, Sri and Hu, Tianyi and Wang, Weimin and Opis-Basilio, Amanda and Ray, Kallol and Dick, Kimberly A. and Pullerits, Tönu and Liu, Maning}},
  issn         = {{2688-4062}},
  language     = {{eng}},
  month        = {{06}},
  number       = {{10}},
  publisher    = {{Wiley}},
  series       = {{Small Structures}},
  title        = {{M(III) Site-Driven Structural Engineering on Lead-Free Layered Double Perovskite Nanocrystals with Enhanced Photoelectrochemical Activity}},
  url          = {{http://dx.doi.org/10.1002/sstr.202500179}},
  doi          = {{10.1002/sstr.202500179}},
  volume       = {{6}},
  year         = {{2025}},
}