arXiv subjects

Jordi Llusar

Publications and source records attributed to Jordi Llusar.

8 recordsLinked to original sources

arXiv2026

Metal-free heteroatom doping of carbon nitride for enhanced photocatalytic hydrogen peroxide production

The photocatalytic production of hydrogen peroxide (H$_2$O$_2$) from water is a promising strategy for solar-to-chemical energy conversion. Herein, we investigate the effect of metal-free heteroatom doping (B, O, P, and S) on the structural, electronic, and photocatalytic properties of graphitic carbon nitride (C$_3$N$_4$) for H$_2$O$_2$ production under simulated solar irradiation. While pristine C$_3$N$_4$ exhibits stacked nanosheets, doping induces disorder, partial exfoliation, and changes in interlayer spacing, confirming successful heteroatom incorporation and modification of the electronic and optical properties. Photocatalytic experiments reveal that H$_2$O$_2$ production strongly depends on the sacrificial agent, pH, and reactive-species scavengers. All doped catalysts show enhanced activity compared to pristine C$_3$N$_4$, with 9.6-, 14.8-, 11.0-, and 16.4-fold increases for B-, P-, O-, and S-doped C$_3$N$_4$, respectively. S-doped C$_3$N$_4$ achieved the highest H$_2$O$_2$ production rate of 3022.1 $μ$mol h$^{-1}$ g$^{-1}$ and an apparent quantum yield of 8.1\%, attributed to improved charge separation and optimized selectivity. Mechanistic studies indicate that oxygen activation mainly follows a two-electron (2e$^{-}$) pathway driven by charge-carrier modulation and reactive oxygen species dynamics, with singlet oxygen and photogenerated holes playing a dominant role. In addition, S-doped C$_3$N$_4$ retained over 95\% of its activity after five cycles. These results highlight metal-free heteroatom doping as an effective strategy for sustainable photocatalytic H$_2$O$_2$ generation.

cond-mat.mtrl-sci↗

arXiv2026

Charge Transfer from Perovskite Quantum Dots to Multifunctional Ligands with Tethered Molecular Species

Perovskite quantum dots (pQDs) are promising materials for optoelectronic and photocatalytic applications due to their unique optical properties. To enhance charge carrier extraction or injection donor/acceptor molecules can be tethered to the pQD. These molecules must strongly bind to the ionic surfaces of pQDs without compromising colloidal stability. These we achieve by using multifunctional ligands containing a quaternary ammonium binding group for strong pQDs surface attachment, a long tail group for colloidal stability, and a functional group near the pQD surface. Such pQDs with ferrocene-functionalized ligands show fast photoexcited hole transfer with near-unity efficiency. Density functional theory calculations reveal how ferrocene's molecular structure reorganizes following hole transfer, affecting its charge separation efficiency. This approach can also be extended to in photoexcited electron and energy transfer processes with pQDs. Therefore, this strategy offers a blueprint for creating efficient QD-molecular hybrids for applications like photocatalysis.

cond-mat.mtrl-sci↗

arXiv2026

Interfacial Reconstructions and Engineering in III-V@II-VI Core-Shell Quantum Dots

In core/shell quantum dots (QDs), the interface between semiconductors of different chemical character largely determines their optoelectronic properties. In III-V/II-VI systems, this boundary involves pronounced chemical and electronic discontinuities that can generate trap states even under complete surface passivation. Using density functional theory on atomistic models of InAs/CdSe QDs, we systematically reconstruct atomic arrangements at the surface and interface to evaluate how local coordination and interfacial dipoles influence the electronic structure. Abrupt interfaces induce charge imbalance and band-gap collapse, whereas introducing an alloyed interlayer that mixes core and shell atoms and vacancies restores energetic alignment and yields delocalized band-edge states, consistent with experimental findings. We also introduce a charge-flow analysis that quantifies charge redistribution across the QD, providing a framework for realistic modeling of interlayer formation and predictive design of defect-free interfaces in core@shell architectures.

cond-mat.mtrl-sci↗

arXiv2026

Fuzzy band structure of quantum dots by Bloch Orbital Expansion, unconventional insights into geometry-electronic structure relations

The extension of ab-initio methods like density functional theory (DFT) to quantum dot (QD) geometries has enabled researchers to explore relationships between QD surface termination and electronic structure. However, fully utilizing the data from DFT requires novel classification methods for QD orbitals. Here, we identify relationships between QD geometry and electronic structure by transforming real-space QD orbitals into momentum-space using Bloch orbital expansion (BOE), yielding a fuzzy QD band structure. Comparing with bulk band structures, we show that truncated, unpassivated facets in III-V and II-VI QDs produce mid-gap orbitals derived from bulk surface orbitals; an identification challenging in real space. QDs with reconstructed facets, however, feature delocalized orbitals formed by superposition of bulk Bloch orbitals. Moreover, we prepare for the first time atomistic core/shell QD models and by the BOE expansion we can clearly identify the core/shell band alignment not possible in real space. These findings emphasize BOE as a vital tool for connecting computational and experimental insights in nanocrystal research.

cond-mat.mtrl-sci↗

arXiv2024

Trions Stimulate Electronic Coupling in Colloidal Quantum Dot Molecules

Recent synthetic progress has enabled the controlled fusion of colloidal CdSe/CdS quantum dots in order to form dimers manifesting electronic coupling in their optical response. While this ``artificial H2 molecule'' constitutes a milestone towards the development of nanocrystal chemistry, the strength of the coupling has proven to be smaller than intended. The reason is that, when an exciton is photo-induced in the system, the hole localizes inside the CdSe cores and captures the electron, thus preventing its delocalization all over the dimer. Here, we predict, by means of k$\cdot$p theory and configuration interaction calculations, that using trions instead of neutral excitons or biexcitons restores the electron delocalization. Positive trions are particularly apt because the strong hole-hole repulsion makes electron delocalization robust against moderate asymmetries in the cores, thus keeping a homodimer-like behavior. Trion-charged colloidal quantum dot molecules have the potential to display quantum entanglement features at room temperature with existing technology.

cond-mat.mes-hall↗

arXiv2024

Ultrafast nanocomposite scintillators based on Cd-enhanced CsPbCl3 nanocrystals in polymer matrix

Lead halide perovskite nanocrystals (LHP-NCs) embedded in polymer matrices are gaining traction for next-generation radiation detectors. While progress has been made on green-emitting CsPbBr3 NCs, scant attention has been given to the scintillation properties of CsPbCl3 NCs, which emit size-tunable UV-blue light matching the peak efficiency of ultrafast photodetectors. In this study, we explore the scintillation characteristics of CsPbCl3 NCs produced through a scalable method and treated with CdCl2. Spectroscopic, radiometric and theoretical analysis on both untreated and treated NCs uncover deep hole trap states due to surface undercoordinated chloride ions, eliminated by Pb to Cd substitution. This yields near-perfect efficiency and resistance to polyacrylate mass-polymerization. Radiation hardness tests demonstrate stability to high gamma doses while time-resolved experiments reveal ultrafast radioluminescence with an average lifetime as short as 210 ps. These findings enhance our comprehension of LHP NCs' scintillation properties, positioning CsPbCl3 as a promising alternative to conventional fast scintillators.

cond-mat.mtrl-sci↗

arXiv2021

Charging of colloidal nanoplatelets: effect of Coulomb repulsion on spin and optoelectronic properties

Colloidal semiconductor nanoplatelets combine weak lateral confinement with strong Coulomb interactions, enhanced by dielectric confinement. When the platelets are charged with carriers of the same sign, this results in severe Coulomb repulsions which shape the electronic structure. To illustrate this point, the shell filling of type-I (CdSe/CdS) and type-II (CdSe/CdTe) core/crown nanoplatelets with up to 4 electrons or holes is investigated theoretically. We find that Coulomb repulsions enable addition energies exceeding room temperature thermal energy and promote the occupation of high-spin states. For charged excitons and biexcitons in CdSe/CdTe nanoplatelets, the repulsions further give rise to multi-peaked emission spectra with widely tunable (over 100 meV) energy, and a transition from type-II to quasi-type-II band profile as the number of electrons confined in the core increases. We conclude that the number of excess carriers injected in nanoplatelets is a versatile degree of freedom to modulate their magnetic and optoelectronic properties.

cond-mat.mes-hall↗

arXiv2020

Nature and Control of Shakeup Processes in Colloidal Nanoplatelets

Recent experiments suggest that the photoluminescence line width of CdSe and CdSe/CdS nanoplatelets (NPLs) may be broadened by the presence of shakeup (SU) lines from negatively charged trions. We carry out a theoretical analysis, based on effective mass and configuration interaction (CI) simulations, to identify the physical conditions that enable such processes. We confirm that trions in colloidal NPLs are susceptible of presenting SU lines up to one order of magnitude stronger than in epitaxial quantum wells, stimulated by dielectric confinement. For these processes to take place trions must be weakly bound to off-centered impurities, which relax symmetry selection rules. Charges on the lateral sidewalls are particularly efficient to this end. We propose that the broad line width reported for core/shell CdSe/CdS NPLs may relate not only to SU processes but also to a metastable spin triplet trion state. Understanding the origin of SU processes opens paths to rational design of NPLs with narrower line width.

cond-mat.mtrl-sci↗