Effects of processing on the stability of molybdenum oxide ultra-thin films

The effects of wet chemical processing conventionally employed in device fabrication standards are systematically studied on molybdenum oxide (MoOx) ultra-thin films. We have combined x-ray photoelectron spectroscopy (XPS), angle resolved XPS and x-ray reflectivity techniques to provide deep insights into the changes in composition, structure and electronic states upon treatment of films with different initial stoichiometry prepared by reactive sputtering. Our results show significant reduction effects associated with the development of gap states in MoOx, as well as changes in the composition, density and structure of the films, systematically correlated with the initial oxidation state of Mo.Comment: 16 pages, 5 figures, Appendix include

Effects of Dielectric Stoichiometry on the Photoluminescence Properties of Encapsulated WSe2 Monolayers

Two-dimensional transition-metal-dichalcogenide semiconductors have emerged as promising candidates for optoelectronic devices with unprecedented properties and ultra-compact performances. However atomically thin materials are highly sensitive to surrounding dielectric media, which imposes severe limitations to their practical applicability. Hence for their suitable integration into devices, the development of reliable encapsulation procedures that preserve their physical properties are required. Here, the excitonic photoluminescence of WSe2 monolayer flakes is assessed, at room temperature and 10 K, on mechanically exfoliated flakes encapsulated with SiOx and AlxOy layers employing chemical and physical deposition techniques. Conformal flakes coating on untreated - non-functionalized - flakes is successfully demonstrated by all the techniques except for atomic layer deposition, where a cluster-like oxide coating is observed. No significant compositional or strain state changes in the flakes are detected upon encapsulation by any of the techniques. Remarkably, our results evidence that the flakes' optical emission is strongly influenced by the quality of the encapsulating oxide - stoichiometry -. When the encapsulation is carried out with slightly sub-stoichiometric oxides two remarkable phenomena are observed. First, there is a clear electrical doping of the monolayers that is revealed through a dominant trion - charged exciton - room-temperature photoluminescence. Second, a strong decrease of the monolayers optical emission is measured attributed to non-radiative recombination processes and/or carriers transfer from the flake to the oxide. Power- and temperature-dependent photoluminescence measurements further confirm that stoichiometric oxides obtained by physical deposition lead to a successful encapsulation.Comment: 30 pages, 6 figure

Anisotropy of the electric field gradient in two-dimensional alpha-MoO_(3) investigated by (57)^Mn((57)^Fe) emission mossbauer spectroscopy

Van der Waals alpha-MoO_(3) samples offer awide range of attractive catalytic, electronic, and optical properties. We present herein an emission Mossbauer spectroscopy (eMS) study of the electric-field gradient (EFG) anisotropy in crystalline free-standing alpha-MoO_(3) samples. Although alpha-MoO3 is a twodimensional (2D) material, scanning electron microscopy shows that the crystals are 0.5-5-mu m thick. The combination of X-ray diffraction and micro-Raman spectroscopy, performed after sample preparation, provided evidence of the phase purity and crystal quality of the samples. The eMS measurements were conducted following the implantation of (57)^Mn (t(1/ 2) = 1.5 min), which decays to the (57)^Fe, 14.4 keV Mossbauer state. The eMS spectra of the samples are dominated by a paramagnetic doublet (D1) with an angular dependence, pointing to the Fe^(2+) probe ions being in a crystalline environment. It is attributed to an asymmetric EFG at the eMS probe site originating from strong in-plane covalent bonds and weak out-of-plane van derWaals interactions in the 2D material. Moreover, a second broad component, D2, can be assigned to Fe^(3+) defects that are dynamically generated during the online measurements. The results are compared to ab initio simulations and are discussed in terms of the in-plane and out-of-plane interactions in the syste

Unusual charge states and lattice sites of Fe in Al x Ga1-x N:Mn

Charge states and lattice sites of Fe ions in virgin and Mn-doped Al x Ga1-x N samples were investigated using Fe-57 emission Mossbauer spectroscopy following radioactive Mn-57(+) ion implantation at ISOLDE, CERN. In the undoped Al x Ga1-x N, Fe2+ on Al/Ga sites associated with nitrogen vacancies and Fe3+ on substitutional Al/Ga sites are identified. With Mn doping, the contribution of Fe3+ is considerably reduced and replaced instead by a corresponding emergence of a single-line-like component consistent with Fe4+ on Al/Ga sites. Density functional theory calculations confirm the Fe4+ charge state as stabilised by the presence of substitutional Mn2+ in its vicinity. The completely filled spin up orbitals in Mn2+ (3d(5)) are expected to enhance magnetic exchange interactions. The population of the Fe4+ state is less pronounced at high Al concentration in Al x Ga1-x N:Mn, a behaviour attributable to hybridisation effects of 3d states to the semiconductor bands which weakens with increasing (decreasing) Al (Ga) content. Our results demonstrate that co-doping promotes the co-existence of unusual charge states of Fe4+ and Mn2+, whereas their trivalent charge states prevail with either transition metal incorporated independently in III-nitrides. Co-doping thus opens up a new avenue for tailoring novel magnetic properties in doped semiconductors.This work was supported by the European Union Seventh Framework through ENSAR (Contract No. 262010) and the German BMBF under Contract Nos. 05K13TSA and 05K16PGA. The work was funded by the Austrian Science Fund (FWF) through Projects No. P26830 and No. P31423. H Masenda, K Bharuth-Ram, and D Naidoo acknowledge support from the South African National Research Foundation and the Department of Science and Innovation within the SA-CERN programme. H Masenda also acknowledges support from the Alexander von Humboldt (AvH) Foundation. B Qi, H P Gislason and S lafsson acknowledge support from the Icelandic Research Fund. I Unzueta thanks the support of (MINECO/FEDER) and the Basque Government for the Grants RTI2018-094683-B-C5 (4, 5) and IT-1005-16, respectively

Anisotropy of the electric field gradient in two-dimensional α-MoO3 investigated by 57Mn(57Fe) emission Mössbauer spectroscopy

Van der Waals α-MoO3 samples offer a wide range of attractive catalytic, electronic, and optical properties. We present herein an emission Mössbauer spectroscopy (eMS) study of the electric-field gradient (EFG) anisotropy in crystalline free-standing α-MoO3 samples. Although α-MoO3 is a two-dimensional (2D) material, scanning electron microscopy shows that the crystals are 0.5-5-µm thick. The combination of X-ray diffraction and micro-Raman spectroscopy, performed after sample preparation, provided evidence of the phase purity and crystal quality of the samples. The eMS measurements were conducted following the implantation of 57Mn (t1/2 = 1.5 min), which decays to the 57Fe, 14.4 keV Mössbauer state. The eMS spectra of the samples are dominated by a paramagnetic doublet (D1) with an angular dependence, pointing to the Fe2+ probe ions being in a crystalline environment. It is attributed to an asymmetric EFG at the eMS probe site originating from strong in-plane covalent bonds and weak out-of-plane van der Waals interactions in the 2D material. Moreover, a second broad component, D2, can be assigned to Fe3+ defects that are dynamically generated during the online measurements. The results are compared to ab initio simulations and are discussed in terms of the in-plane and out-of-plane interactions in the system