Tönu Pullerits
Professor
M(III) Site-Driven Structural Engineering on Lead-Free Layered Double Perovskite Nanocrystals with Enhanced Photoelectrochemical Activity
Author
Summary, in English
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.
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.
Department/s
- LU Profile Area: Light and Materials
- NanoLund: Centre for Nanoscience
- Centre for Analysis and Synthesis
- LTH Profile Area: Photon Science and Technology
- LTH Profile Area: Nanoscience and Semiconductor Technology
- Chemical Physics
- MAX IV Laboratory
Publishing year
2025-06-29
Language
English
Publication/Series
Small Structures
Volume
6
Issue
10
Document type
Journal article
Publisher
Wiley
Topic
- Materials Chemistry
Status
Published
ISBN/ISSN/Other
- ISSN: 2688-4062