Alloying multiple halide perovskites on the same sublattice in search of stability and target band gaps

Journal Article · Fri Jun 06 00:00:00 EDT 2025 · Materials Horizons

DOI:https://doi.org/10.1039/D5MH00540J· OSTI ID:3021645

Sabino, Fernando P. ^[1]; Xiong, Jia-Xin ^[2]; Zhang, Xiuwen ^[2]; Dalpian, Gustavo M. ^[3]; Zunger, Alex ^[2]

---

1. University of São Paulo, São Carlos (Brazil); University of Colorado, Boulder, CO (United States); University of São Paulo (Brazil)
2. University of Colorado, Boulder, CO (United States)
3. University of São Paulo (Brazil)

Single-component halide perovskites (HPs) rarely satisfy all the necessary criteria for optoelectronic applications, such as achieving an optimal band gap while maintaining high chemical and structural stability. Alloying halide perovskites has emerged as a promising strategy, not only to enhance stability but also to fine-tune their electronic and optical properties. In this work, we explore multiple degrees of freedom in alloy design, considering different substitution sublattices sites (A, B, or X in ABX3 perovskites), various chemical species (isovalent and hetero-valent elements), and multi-component compositions on a given sublattice. Using first-principles calculations based on density functional theory (DFT), we investigate how compositional variations influence the electronic (band gap) and structural properties (mixing enthalpy) of HP alloys. Our approach employs the polymorphous cell model, allowing full local relaxation which breaks local symmetry while preserving global cubic symmetry—an essential framework for accurately modeling HPs. Our results reveal that X-site mixing (halogen substitution) primarily affects the valence band maximum, allowing target band gap engineering. Additionally, variations in halogen radii introduce internal strain through octahedral distortions, influencing the mixing enthalpy. A-site substitution, while not directly contributing to the band edge states, modifies structural stability via volume effects, indirectly impacting the band gap. B-site alloying plays a dominant role in band gap modulation, leading to either positive or negative band gap bowing. Specifically, isovalent B-site mixing (Sn–Pb) induces strong positive bowing, where the alloy band gap is smaller than the average gap of parent compounds, whereas hetero-valent mixing (Cd–Pb) results in pronounced negative bowing. As an aside, we investigate the competition between the excess energy of disordered alloys vs. that of long-range ordered double perovskites of the same compositions, seeking examples of ordered phases emerging from disordered alloys. Furthermore, our findings provide fundamental insights into the electronic and structural behavior of HP alloys, offering valuable design principles for the development of stable and efficient materials for next-generation photovoltaic and optoelectronic devices.

• Research Organization: University of Colorado, Boulder, CO (United States)
• Sponsoring Organization: FAPESP; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
• Grant/Contract Number: EE0009515; EE0009615
• Other Award/Contract Number: 2021/14422-0; 2021/11786-1; 23/09820-2
• OSTI ID: 3021645
• Journal Information: Materials Horizons, Journal Name: Materials Horizons Journal Issue: 18 Vol. 12; ISSN 2051-6355; ISSN 2051-6347
• Publisher: Royal Society of Chemistry
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY
36 MATERIALS SCIENCE
Electronic structure
Halide perovskites
Halide perovskites alloys
Multi-component alloys