Cited by 23Advanced Photocatalysis TechniquesIron oxide chemistry and applicationsElectronic and Structural Properties of Oxides

Thickness-Dependent Photoelectrochemical Water Splitting Properties of Self-Assembled Nanostructured LaFeO3 Perovskite Thin Films

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Andrei, Florin, Ion, Valentin, Bîrjega, Ruxandra, Dinescu, Maria, Enea, Nicoleta, Pantelica, Dan, Mihai, Maria Diana, Maraloiu, Valentin-Adrian +3 more·2021·Nanomaterials

Abstract

Tuning the intrinsic structural and stoichiometric properties by different means is used for increasing the green energy production efficiency of complex oxide materials. Here, we report on the formation of self-assembled nanodomains and their effects on the photoelectrochemical (PEC) properties of LaFeO3 (LFO) epitaxial thin films as a function of layer’s thickness. The variation with the film’s thickness of the structural parameters such as in-plane and out-of-plane crystalline coherence length and the coexistence of different epitaxial orientation—<100>SrTiO3//<001> LFO, <100>SrTiO3//<110> LFO and [110] LFO//[10] STO, as well as the appearance of self-assembled nanodomains for film’s thicknesses higher than 14 nm, is presented. LFO thin films exhibit different epitaxial orientations depending on their thickness, and the appearance of self-assembled nanopyramids-like domains after a thickness threshold value has proven to have a detrimental effect on the PEC functional properties. Using Nb:SrTiO3 as conductive substrate and 0.5 M NaOH aqueous solution for PEC measurements, the dependence of the photocurrent density and the onset potential vs. RHE on the structural and stoichiometric features exhibited by the LFO photoelectrodes are unveiled by the X-ray diffraction, high-resolution transmission electron microscopy, ellipsometry, and Rutherford backscattering spectroscopy results. The potentiodynamic PEC analysis has revealed the highest photocurrent density Jphotocurrent values (up to 1.2 mA/cm2) with excellent stability over time, for the thinnest LFO/Nb:SrTiO3 sample, both cathodic and anodic behavior being noticed. Noticeably, the LFO thin film shows unbiased hydrogen evolution from water, as determined by gas chromatography in aqueous 0.5 M NaOH solution under constant illumination.

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Crossref · 10.3390/nano11061371

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  • Strain gradients can be induced into film thickness by growing compositionally graded heterostructures through dopants, where lattice parameter evolution imposes chemical pressure as a driving force for the strain gradient.

    “For example, different from the conventional epitaxial misfit homogenous strain induced in ferroelectric or multiferroic thin films, strain gradients can be induced into the film thickness by growing compositionally graded heterostructures through dopants [222,223], where the evolution of the lattice parameter with composition variation will impose a 'chemical pressure' as a driving force for the”

    From Metal Oxide Thin Films for Advanced Photonic Applications (2026) · cites this paper as [223]

    The Introduction (page not supplied) says that doping can affect the formation of nanostructured heteroepitaxial films. The XRD Results (page not supplied) report lattice-parameter and microstrain changes with film thickness. Neither passage establishes that compositionally graded dopants create a through-thickness strain gradient driven by chemical pressure. (LLM, conf=0.78)

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Authors
Andrei, F., Ion, V., Bîrjega, R., Dinescu, M., Enea, N., Pantelica, D., Mihai, M. D., Maraloiu, V.-A., Teodorescu, V. S., Marcu, I.-C., & Scarisoreanu, N. D.
Affiliations
  • University of Bucharest (RO)
  • National Institute for Laser Plasma and Radiation Physics (RO)
  • National Institute for Laser, Plasma and Radiation Physics, 077125 Magurele, Romania
  • Horia Hulubei National Institute for R and D in Physics and Nuclear Engineering (RO)
  • National Institute of Materials Physics (RO)
  • Academia Oamenilor de Știință din România (RO)
Corresponding author
  • Marcu, Ioan-Cezar
  • Scarisoreanu, Nicu Doinel
Venue
Nanomaterials
Publisher
MDPI AG
Published
2021-05-21
Volume
11
Issue
6
Pages
1371
ISSN
2079-4991 (ISSN-L)
OpenAlex
W3160946449
Cited by
22
References
57
Citations by year
2026: 2 · 2025: 5 · 2024: 4 · 2023: 3 · 2022: 3 · 2021: 5
FWCI
0.70
Type
journal article
Language
en
Open access
Locations
  • Nanomaterials (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Funders
Unitatea Executiva pentru Finantarea Invatamantului Superior, a Cercetarii, Dezvoltarii si Inovarii (PCE95 -I D-PCE-2016-0911)
Topics
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Advanced Photocatalysis Techniques
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Iron oxide chemistry and applications
  • Physical Sciences › Materials Science › Materials Chemistry › Electronic and Structural Properties of Oxides
Keywords
LaFeO3, perovskite thin films, photoelectrochemical water splitting, film thickness dependence, epitaxial orientation, SrTiO3 substrate, Nb-doped SrTiO3, hydrogen evolution reaction, photocurrent density, turn-on voltage, stoichiometry, nanopyramids

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