Juan F. Sánchez-Royo

Electronic structure, optical properties, and lattice dynamics in atomically thin indium selenide flakes

The progressive stacking of chalcogenide single layers gives rise to two-dimensional semiconducting materials with tunable properties that can be exploited for new field-effect transistors and photonic devices. Yet the properties of some members of the chalcogenide family remain unexplored. Indium selenide (InSe) is attractive for applications due to its direct bandgap in the near infrared, controllable p- and n-type doping and high chemical stability. Here, we reveal the lattice dynamics, optical and electronic properties of atomically thin InSe flakes prepared by micromechanical cleavage. Raman active modes stiffen or soften in the flakes depending on which electronic bonds are excited. A progressive blue-shift of the photoluminescence peaks is observed for decreasing flake thickness (as large as 0.2 eV for three single layers). First-principles calculations predict an even larger increase in the bandgap, 0.40 eV, for three single layers, and as much as 1.1 eV for a single layer. These results are promising from the point of view of the versatility of this material for optoelectronic applications at the nanometer scale and compatible with Si and III-V technologies.

Thin film growth and band lineup of In2O3 on the layered semiconductor InSe

Thin films of the transparent conducting oxide In2O3 have been prepared in ultrahigh vacuum by reactive evaporation of indium. X-ray diffraction, optical, and electrical measurements were used to characterize properties of films deposited on transparent insulating mica substrates under variation of the oxygen pressure. Photoelectron spectroscopy was used to investigate in situ the interface formation between In2O3 and the layered semiconductor InSe. For thick In2O3 films a work function of φ=4.3 eV and a surface Fermi level position of EF−EV=3.0 eV is determined, giving an ionization potential IP=7.3 eV and an electron affinity χ=3.7 eV. The interface exhibits a type I band alignment with ΔEV=2.05 eV, ΔEC=0.29 eV, and an interface dipole of δ=−0.55 eV.

Nanotexturing To Enhance Photoluminescent Response of Atomically Thin Indium Selenide with Highly Tunable Band Gap.

Manipulating properties of matter at the nanoscale is the essence of nanotechnology, which has enabled the realization of quantum dots, nanotubes, metamaterials, and two-dimensional materials with tailored electronic and optical properties. Two-dimensional semiconductors have revealed promising perspectives in nanotechnology. However, the tunability of their physical properties is challenging for semiconductors studied until now. Here we show the ability of morphological manipulation strategies, such as nanotexturing or, at the limit, important surface roughness, to enhance light absorption and the luminescent response of atomically thin indium selenide nanosheets. Besides, quantum-size confinement effects make this two-dimensional semiconductor to exhibit one of the largest band gap tunability ranges observed in a two-dimensional semiconductor: from infrared, in bulk material, to visible wavelengths, at the single layer. These results are relevant for the design of new optoelectronic devices, including heterostructures of two-dimensional materials with optimized band gap functionalities and in-plane heterojunctions with minimal junction defect density.

Highly fluorescent and photostable organic- and water-soluble CdSe/ZnS core-shell quantum dots capped with thiols

Highly fluorescent organic- and water-soluble CdSe/ZnS core-shell quantum dots (QDs) with thiol ligands chemisorbed on the QD surface were synthesized by the replacement of amine ligands by alkyl thiols under very mild conditions. The QDs exhibited an even greater photostability than the initial core-shell amine capped QDs.

Optical and photovoltaic properties of indium selenide thin films prepared by van der Waals epitaxy

Indium selenide thin films have been grown on p-type gallium selenide single crystal substrates by van der Waals epitaxy. The use of two crucibles in the growth process has resulted in indium selenide films with physical properties closer to these of bulk indium selenide than those prepared by other techniques. The optical properties of the films have been studied by electroabsorption measurements. The band gap and its temperature dependence are very close to those of indium selenide single crystals. The width of the fundamental transition, even if larger than that of the pure single crystal material, decreases monotonously with temperature. Exciton peaks are not observed even at low temperature, which reveals that these layers still contain a large defect concentration. The current–voltage characteristic of indium selenide thin film devices was measured under simulated AM2 conditions. The solar conversion efficiency of these devices is lower than 0.6%. The high concentration of defects reduces the diffusion length of minority carriers down to values round to 0.2 μm.

Reversible chemisorption of sulfur dioxide in a spin crossover porous coordination polymer.

The chemisorption of sulfur dioxide (SO2) on the Hofmann-like spin crossover porous coordination polymer (SCO-PCP) {Fe(pz)[Pt(CN)4]} has been investigated at room temperature. Thermal analysis and adsorption-desorption isotherms showed that ca. 1 mol of SO2 per mol of {Fe(pz)[Pt(CN)4]} was retained in the pores. Nevertheless, the SO2 was loosely attached to the walls of the host network and completely released in 24 h at 298 K. Single crystals of {Fe(pz)[Pt(CN)4]}·nSO2 (n ≈ 0.25) were grown in water solutions saturated with SO2, and its crystal structure was analyzed at 120 K. The SO2 molecule is coordinated to the Pt(II) ion through the sulfur atom ion, Pt-S = 2.585(4) Å. This coordination slightly stabilizes the low-spin state of the Fe(II) ions shifting the critical temperatures of the spin transition by 8-12 K. DFT calculations have been performed to rationalize these observations.

Femtosecond laser fragmentation from water-dispersed microcolloids: toward fast controllable growth of ultrapure Si-based nanomaterials for biological applications

An ultrashort laser-assisted method for fast production of concentrated aqueous solutions of ultrapure Si-based colloidal nanoparticles is reported. The method profits from the 3D geometry of femtosecond laser ablation of water-dispersed microscale colloids, prepared preliminarily by the mechanical milling of a Si wafer, in order to avoid strong concentration gradients in the ablated material and provide similar conditions of nanocluster growth within a relatively large laser caustics volume. We demonstrate the possibility for the fast synthesis of non-aggregated, low-size-dispersed, crystalline Si-based nanoparticles, whose size and surface oxidation can be controlled by changing the initial microcolloid concentration and the amount of dissolved oxygen in the water. Due to their much superior purity compared to the chemically synthesized counterparts and their photoluminescence response, the nanoparticles present the possibility for biological in vivo applications such as drug vectoring, imaging, and therapeutics.

Layered double hydroxide (LDH)–organic hybrids as precursors for low-temperature chemical synthesis of carbon nanoforms

A low-temperature route for the chemical synthesis of diverse carbon nanoforms, including nano-onions and multi-walled nanotubes, is described. The method involves thermal decomposition of a sebacate-intercalated NiFe LDH at 400 °C and benefits from the catalytic activity of FeNi3 nanoparticles generated in situ.

Tin-related double acceptors in gallium selenide single crystals

Gallium selenide single crystals doped with different amounts of tin are studied through resistivity and Hall effect measurements in the temperature range from 30 to 700 K. At low doping concentration tin is shown to behave as a double acceptor impurity in gallium selenide with ionization energies of 155 and 310 meV. At higher doping concentration tin also introduces deep donor levels, but the material remains p-type in the whole studied range of tin doping concentrations. The deep character of donors in gallium selenide is discussed by comparison of its conduction band structure to that of indium selenide under pressure. The double acceptor center is proposed to be a tin atom in interlayer position, with a local configuration that is similar to that of tin diselenide. The hole mobility exhibits an anomalous dependence on the tin content, attaining its maximum value in the ingot with 0.2% nominal tin content. This is proposed to be related to impurity pairing effects giving rise to thermal shallow accepto...

Photovoltaic properties of indium selenide thin films prepared by van der Waals epitaxy

Abstract Indium selenide thin films have been grown on gallium selenide single crystal substrates by van der Waals epitaxy. Low energy electron diffraction patterns show that the film grows with the substrate orientation and its valence band photoemission spectrum exhibits the same structure as single crystals. The film absorption edge has been studied through the photovoltaic spectra as a function of temperature. The optical gap value and its temperature dependence are those measured in bulk indium selenide, but exciton peaks are not observed even at low temperature, which reveals a large defect concentration.