Large area TMD-based van der Waals heterostructures featuring enhanced photoconversion in the flat optics regime

One of the most urgent technological needs of this century concerns the research of innovative nanomaterials for applications in optoelectronics, nanophotonics and photovoltaics for renewable energy conversion. In fact, downscaling of the silicon-based devices (e.g. field-effect transistors) has come to an end due to intrinsic physical limitations such as size, inadequate carrier mobility, short channel effects, atomic-scale interactions, heat generation, and energy consumption at atomic scale thickness, requiring innovative materials to overcome such difficulties. Graphene discovery in 2004 by Novoselov and Geim arose a tremendous interest for the two-dimensional (2D) materials, in which the reduced dimensionality brings new properties with respect to their bulk counterparts. Despite the extraordinary properties exhibited by graphene, its gapless nature strongly limits the fabrication of graphene-based optoelectronic devices. For this reason, the interest of researchers shifted towards the class of 2D semiconductors. Among these materials, Transition Metal Dichalcogenides (TMDs) represent the most important family due to suitable bandgap energy values which match the Schockley-Queisser efficiency criterion for solar photoconversion, and to their extraordinary optical absorption coefficient. Additionally, 2D materials can be vertically stacked to form the so-called van der Waals heterostructures that are endowed by pristine interface thanks to the relatively weak van der Waals interactions that keep the stack together. This offers the opportunity to fabricate heterostructures of arbitrary 2D materials, independently by their crystal structure, with no limitations on the engineering of the optoelectronic and photonic properties of the new stacked metamaterial. In particular, the possibility to realize van der Waals p-n junctions by coupling 2D-TMDs layers is very intriguing for photoconversion and photovoltaic applications. So far, TMDs employment has been mostly limited to the fabrication of prototypical devices such as field-effect transistors and photodetectors, most of which were realized via mechanical exfoliation from single crystal of flakes with thickness ranging from one to few atomic layers. Despite their intriguing properties, these materials do not represent an industrially relevant alternative to traditional semiconductors, being the exfoliation a randomic process with very low yields and limited areas in the micrometer range. Consequently, one of the key frontiers of TMDs research is the large area growth of homogeneous ultra-thin layers with controlled thickness over macroscopic areas. To meet this requirement, several large area techniques have been studied to synthesize TMDs layers extending over cm² areas. However, in contrast with the exfoliation process, these techniques result in polycrystalline layers where the high concentration of grain boundaries degrades the macroscopic conduction. The second crucial issue to be solved for ultra-thin TMD-based devices to be used in photoconductive and photodetection applications is the maximization of the optical absorption. Despite the excellent optical absorption coefficient, an ultra-thin TMD film indeed cannot absorb efficiently the incoming light due to the ultimately reduced thickness, which means a nanometric optical path. It is thus evident that new strategies for the optical absorption amplification in ultra-thin 2D semiconductors need to be developed to allow proper performances in TMD-based photodetection and photovoltaics applications. Because of the atomic thickness of the 2D layer, traditional solutions developed for the light harvesting amplification in conventional silicon-based photovoltaic devices, based on pyramidal microstructuring or on the addition of antireflective coatings, cannot be transferred to these materials. Recently, the research group where I carried out my activity worked on large area ultra-thin MoS₂ films conformally grown on self-organized rippled substrate fabricated by ion beam sputtering. Their results clearly showed a modification of the TMD optical and electronic properties grown on the nanostructured substrate with respect to a flat one. This observation was explained with the stress induced by the substrate morphology in the MoS₂ layer in correspondence to the high curvature regions given by the crests and valleys of the ripples, meaning that by control of the substrate morphology it is possible to engineer the material intrinsic properties. Additionally, the nanostructures anisotropy adds a polarization-dependent optical response, offering a way to engineer the optical absorption of the 2D material in view of photoconversion applications. However, self-organized nanostructures suffer from a relevant size dispersion and long range disorder, whereas more interesting optical effects are expected for periodic nanogratings in which the subwavelength TMD layers reshaping provide them the functionality of flat optic diffractive elements. Starting from here, I devoted the most of my research activity to face the two main challenges described above: developing a growth process for large area ultra-thin TMD films, and studying an efficient light harvesting strategy to maximize the optical absorption in few-layer semiconductor films. An overview of the state-of-the-art regarding 2D materials and nanophotonics approaches for light harvesting in ultra-thin films is given in Chapter 1, while the growth synthesis techniques are postponed in Chapter 2. At the beginning of my PhD, MoS₂ films were grown by external collaborators of my group, thus limiting the activities. In the first phase of my research activity, I developed a novel large area growth process based on the physical deposition of solid precursor films and sulfurization, as I will describe in Chapter 2. This novel technique enabled not only the in-house growth of ultra-thin MoS₂ films for the first time, but also allowed to extend the process to ultra-thin WS₂ layers. Having now the capability to control the deposition of two different TMDs layers, I moved to the growth of large area van der Waals heterostructures. Due to the type-II heterojunction formed by the band structure coupling of MoS₂ and WS₂, such heterostructures are expected to have a high potential in photoconversion applications. In Chapter 3 I will show the nanofabrication of planar MoS₂/WS₂ heterostacks, and their application in photocatalytic experiments and in a prototype of photonic device, featuring first evidence of photovoltage and photocurrent under illumination. This latter application also required me to develop large area transparent electrodes, so that I will dedicate a part of the chapter to indium tin oxide thin films and large area graphene. In the second phase of my research activity, I focused on light harvesting in ultra-thin TMDs layers. Thanks to the conformality achieved by the physical deposition process, I explored a nanophotonic approach based on the optical anomalies arising from periodic modulation of the TMD layer at the subwavelength scale, obtained by conformal growth of the TMD layers onto nanostructured substrates. To this end, periodic nanogratings have been used as a template for the growth of ultra-thin MoS₂ layers. Differently from the self-organized nanostructures mentioned before, the periodicity induces diffractive effects that are exploited to steer the light parallel to the active 2D material enhancing the optical absorption, as demonstrated in Chapter 4 both directly by absorption measurements and indirectly by a photo-to-chemical energy conversion experiment where we detected enhanced photocatalytic performances. In the final part of my project, I started preliminary studies on the elastic scattering properties of subwavelength periodical lattices based on nanostructured tilted TMD layers. By defocused ion beam sputtering, I was able to reshape the morphology of the initial nanograting templates to further engineer the TMD optical response. In particular, by off-normal incidence sputtering it is possible to tailor a specific slope of the tilted nanofacets, on top of which I deposited laterally disconnected MoS₂ nanostripes by grazing angle physical deposition. By developing a custom-made scatterometer, optical characterization of ultra-thin MoS₂ nanostripes and thicker MoS₂ films was performed, giving interesting preliminary results on the directional light scattering properties of these reshaped layers, as reported in Chapter 5. Finally, I adopted a similar deposition approach for the nanofabrication of large area heterostructures nanoarrays based on few-layer WS₂ nanostripes coated by a conformal MoS₂ layer, demonstrating further engineering of the optical response of few-layer TMD films with impact in photoconversion

Deterministic Thermal Sculpting of Large-Scale 2D Semiconductor Nanocircuits

Two-dimensional (2D) Transition Metal Dichalcogenide semiconductor (TMDs) nanocircuits are deterministically engineered over large-scale substrates. The original approach combines large-area physical growth of 2D TMDs layer with high resolution thermal - Scanning Probe Lithography (t-SPL), to reshape the ultra-thin semiconducting layers at the nanoscale level. We demonstrate the additive nanofabrication of few-layer MoS2 nanostructures, grown in the 2H-semiconducting TMD phase, as shown by their Raman vibrational fingerprints and by their optoelectronic response. The electronic signatures of the MoS2 nanostructures are locally identified by Kelvin probe force microscopy providing chemical and compositional contrast at the nanometer scale. Finally, the potential role of the 2D TMD nanocircuits as building blocks of deterministic 2D semiconducting interconnections is demonstrated by high-resolution local conductivity maps showing the competitive transport properties of these large-area nanolayers. This work thus provides a powerful approach to scalable nanofabrication of 2D nano-interconnects and van der Waals heterostructures, and to their integration in real-world ultra-compact electronic and photonic nanodevices.Comment: 17 pages, 4 figure

Broadband and Tunable Light Harvesting in Nanorippled MoS2 Ultrathin Films

Nanofabrication of flat optic silica gratings conformally layered with two-dimensional (2D) MoS2 is demonstrated over large area (cm2), achieving a strong amplification of the photon absorption in the active 2D layer. The anisotropic subwavelength silica gratings induce a highly ordered periodic modulation of the MoS2 layer, promoting the excitation of Guided Mode Anomalies (GMA) at the interfaces of the 2D layer. We show the capability to achieve a broadband tuning of these lattice modes from the visible (VIS) to the near-infrared (NIR) by simply tailoring the illumination conditions and/or the period of the lattice. Remarkably, we demonstrate the possibility to strongly confine resonant and nonresonant light into the 2D MoS2 layers via GMA excitation, leading to a strong absorption enhancement as high as 240% relative to a flat continuous MoS2 film. Due to their broadband and tunable photon harvesting capabilities, these large area 2D MoS2 metastructures represent an ideal scalable platform for new generation devices in nanophotonics, photo- detection and -conversion, and quantum technologies

What is the role of the placebo effect for pain relief in neurorehabilitation? Clinical implications from the Italian consensus conference on pain in neurorehabilitation

Background: It is increasingly acknowledged that the outcomes of medical treatments are influenced by the context of the clinical encounter through the mechanisms of the placebo effect. The phenomenon of placebo analgesia might be exploited to maximize the efficacy of neurorehabilitation treatments. Since its intensity varies across neurological disorders, the Italian Consensus Conference on Pain in Neurorehabilitation (ICCP) summarized the studies on this field to provide guidance on its use. Methods: A review of the existing reviews and meta-analyses was performed to assess the magnitude of the placebo effect in disorders that may undergo neurorehabilitation treatment. The search was performed on Pubmed using placebo, pain, and the names of neurological disorders as keywords. Methodological quality was assessed using a pre-existing checklist. Data about the magnitude of the placebo effect were extracted from the included reviews and were commented in a narrative form. Results: 11 articles were included in this review. Placebo treatments showed weak effects in central neuropathic pain (pain reduction from 0.44 to 0.66 on a 0-10 scale) and moderate effects in postherpetic neuralgia (1.16), in diabetic peripheral neuropathy (1.45), and in pain associated to HIV (1.82). Moderate effects were also found on pain due to fibromyalgia and migraine; only weak short-term effects were found in complex regional pain syndrome. Confounding variables might have influenced these results. Clinical implications: These estimates should be interpreted with caution, but underscore that the placebo effect can be exploited in neurorehabilitation programs. It is not necessary to conceal its use from the patient. Knowledge of placebo mechanisms can be used to shape the doctor-patient relationship, to reduce the use of analgesic drugs and to train the patient to become an active agent of the therapy

What is the role of the placebo effect for pain relief in neurorehabilitation? Clinical implications from the Italian Consensus Conference on Pain in Neurorehabilitation

Background: It is increasingly acknowledged that the outcomes of medical treatments are influenced by the context of the clinical encounter through the mechanisms of the placebo effect. The phenomenon of placebo analgesia might be exploited to maximize the efficacy of neurorehabilitation treatments. Since its intensity varies across neurological disorders, the Italian Consensus Conference on Pain in Neurorehabilitation (ICCP) summarized the studies on this field to provide guidance on its use. Methods: A review of the existing reviews and meta-analyses was performed to assess the magnitude of the placebo effect in disorders that may undergo neurorehabilitation treatment. The search was performed on Pubmed using placebo, pain, and the names of neurological disorders as keywords. Methodological quality was assessed using a pre-existing checklist. Data about the magnitude of the placebo effect were extracted from the included reviews and were commented in a narrative form. Results: 11 articles were included in this review. Placebo treatments showed weak effects in central neuropathic pain (pain reduction from 0.44 to 0.66 on a 0-10 scale) and moderate effects in postherpetic neuralgia (1.16), in diabetic peripheral neuropathy (1.45), and in pain associated to HIV (1.82). Moderate effects were also found on pain due to fibromyalgia and migraine; only weak short-term effects were found in complex regional pain syndrome. Confounding variables might have influenced these results. Clinical implications: These estimates should be interpreted with caution, but underscore that the placebo effect can be exploited in neurorehabilitation programs. It is not necessary to conceal its use from the patient. Knowledge of placebo mechanisms can be used to shape the doctor-patient relationship, to reduce the use of analgesic drugs and to train the patient to become an active agent of the therapy

Large scale metasurfaces: from plasmonics to photon harvesting in 2D semiconductor layers

The nanofabrication of large-area metasurfaces with tunable optoelectronic response is crucial in many fields from plasmonics to energy conversion. Here the engineering of self-organized plasmonic antennas will be demonstrated, showing their performances in photo-degradation of polluting molecules. In parallel, the capability to strongly couple light to large-area 2D semiconductor layers will be shown. Thanks to nanoscale re-shaping of the interface to form flat-optics nanogratings superior photon harvesting performances can be achieved with strong impact in photonics and energy conversion.

Plasmonic and 2D-TMD nanoarrays for large-scale photon harvesting and enhanced molecular photo-bleaching

The urgent environmental and energy challenges require novel solutions for efficient light harvesting and conversion in new-generation ultra-thin devices. Plasmonic nanoantennas and flat optics nanogratings can promote light matter interaction at the nanoscale being very attractive for ultra-thin photonics and sensing applications. In this work we developed two light trapping solutions based on large-scale nanomaterials. The first system is a large-scale (cm2) plasmonic metasurface based on self-organized gold nanostripes. The second is based on the periodic re-shaping of ultra-thin semiconducting MoS2 layers forming large-area flat-optics nanogratings. Under this condition Rayleigh Anomalies can be resonantly excited thus promoting in-plane light confinement and photon absorption into the few-layers material. To demonstrate the impact of these nanopatterned systems in photon harvesting we probed their efficiency into a prototypal photochemical reaction: the photo-bleaching of Methylene Blue (MB). We demonstrate the resonant enhancement of the photo-bleaching of these polluting dye molecules promoted either by the localized plasmon resonance in Au nanostripes or by the Rayleigh Anomaly in flat-optics MoS2 nanogratings. We investigate this effect through a quantitative analysis of the solution photodissociation induced by a monochromatic light. These results show the strong potential of flat-optics templates for light-harvesting and energy conversion in ultra-thin photonic devices

Conservative Management of Atypical Endometrial Hyperplasia and Early Endometrial Cancer in Childbearing Age Women

Total hysterectomy and bilateral adnexectomy is the standard treatment for atypical endometrial hyperplasia and early-stage endometrial cancer. However, the recommended surgical treatment precludes future pregnancy when these conditions are diagnosed in women in their fertile age. In these patients, fertility-sparing treatment may be feasible if the desire for childbearing is consistent and specific conditions are present. This review summarizes the available evidence on fertility-sparing management for atypical endometrial hyperplasia and early-stage endometrial cancer. Historically, oral progestins have been the mainstay of conservative management for atypical endometrial hyperplasia and stage IA endometrioid endometrial cancer with no myometrial invasion, although there is no consensus on dosage and treatment length. Intrauterine progestin therapy has proved a valid alternative option when oral progestins are not tolerated. GnRH analogs, metformin, and hysteroscopic resection in combination with progestins appear to increase the overall efficacy of the treatment. After a complete response, conception is recommended; alternatively, maintenance therapy with strict follow-up has been proposed to decrease recurrence. The risk of disease progression is not negligible, and clinicians should not overlook the risk of hereditary forms of the disease in young patients, in particular, Lynch syndrome. Hysterectomy is performed once the desire for childbearing desire has been established. The conservative management of atypical endometrial hyperplasia and early-stage endometrial cancer is feasible, provided a strong desire for childbearing and permitting clinical-pathological conditions. However, patients must be aware of the need for a strict follow-up and the risk of progression with a possible consequent worsening of the prognosis. More homogenous and well-designed studies are necessary to standardize and identify the best treatment and follow-up protocols