Tailoring MoS2 domains size, doping, and light emission by the sulfurization temperature of ultra-thin MoOx films on sapphire

Thermal sulfurization of ultra-thin Mo-based films represents a promising approach for large-area growth of MoS2. In this paper, we demonstrated that the crystalline quality (domains size and defects density), strain, doping, and light emission properties of monolayer (1L) MoS2 obtained from sputter deposited MoOx films on a c-sapphire substrate can be tailored by the sulfurization temperature (Ts) in the range from 700 to 800 °C. Starting from a continuous film with a nanocrystalline domains structure at Ts = 700 °C, a distribution of 1L MoS2 triangular domains with 2.1 ± 0.6 and 2.6 ± 1.6 μm average sizes was obtained by increasing Ts to 750 and 800 °C, respectively. The increase in Ts was accompanied by a strong (25×) enhancement of the photoluminescence (PL) intensity. Furthermore, the average doping of MoS2, evaluated from Raman analyses, evolved from a strong p-type doping (∼1 × 1013 cm−2) after Ts = 700 °C, ascribed to residual MoO3 in the film, to a low average n-type doping (∼0.04 × 1013 cm−2) after Ts = 800 °C. The wide tunability of doping and PL of 1L MoS2 by the sulfurization temperature can be exploited to tailor material properties for different specific applications

Thermal Stability of Monolayer MoS2 Flakes under Controlled Atmosphere

INTRODUCTION Bi-dimensional materials are a novel category of solid-state structures renowned for their enticing mechanical and electronic properties.1 Among these, MoS2 is one of the most investigated members thanks to its stability and its bulk counterpart being largely abundant in nature. Such semiconductor, belonging to the transition metal dichalcogenides family, presents a thickness dependent band-gap which gives — in the case of monolayer MoS2 — strong light-absorption capabilities and intense photoluminescence.2 Such properties as well as its high charge carrier mobility have allowed for the development of optoelectronic devices such as transistors, diodes, photodetectors and light emitting devices.3 Nonetheless, several issues are yet to be faced before considering a more widespread usage of this bi-dimensional semiconductor. In particular, because of its sensitivity to the environment and of the interactions occurring with its substrate, MoS2 is often subject to ageing effects leading to alterations in its mechanical, optical and electronic properties.4 In this context we have studied the effects that thermal treatments carried out in a controlled atmosphere of O2, Ar, N2 as well as air have on the properties of monolayer MoS2 flakes deposited on a gold substrate. By means of characterization techniques such as Raman and optical spectroscopy we have explored the material’s stability and the reversibility of the aging processes. It was found that changes in the stress displayed by the material’s crystalline structure induced during the production or by aging in room atmosphere are tuned by the treatment in the given controlled atmosphere and retained after going back to ambient temperature in a permanent way. Additionally, the characteristic exciton emission bands of monolayer MoS2 are found to shift in position and their relative intensities are found to change both depending on selected gas and aging time. Such studies are aimed at further understanding the structural and electronic effects that processes such as aging and interactions with the external environment have on monolayer MoS2. REFERENCES [1] C. Ferrari, A. et al. “Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems” Nanoscale 7, 4598–4810 (2015). [2] Splendiani, A. et al. “Emerging Photoluminescence in Monolayer MoS2” Nano Lett. 10, 1271–1275 (2010). [3] Singh, E., Singh, P., Kim, K. S., Yeom, G. Y. & Nalwa, H. S. “Flexible Molybdenum Disulfide (MoS2) Atomic Layers for Wearable Electronics and Optoelectronics” ACS Appl. Mater. Interfaces 11, 11061–11105 (2019). [4] Panasci, S. E. et al. “Strain, Doping, and Electronic Transport of Large Area Monolayer MoS2 Exfoliated on Gold and Transferred to an Insulating Substrate” ACS Appl. Mater. Interfaces 13, 31248–31259 (2021)

The effect of verbal encouragement on performance and muscle fatigue in swimming

Background and Objectives: Verbal encouragement (VE) can be used to enhance performance in several sports, even though no studies have been conducted among swimmers and only a few effects have been reported in elite athletes. Besides influencing motor performance, VE is also known to enhance the physical load, thus potentially increasing the probability of developing fatigue. With this in mind, this study aimed to explore the effects of VE in swimmers in order to fill in the knowledge gap concerning the aquatic environment. Materials and Methods: Each athlete swam a maximal 200 m freestyle trial under two different conditions: one trial with VE and the other without VE. The two main outcome measures were: (1) performance velocity (m/s); and (2) muscle fatigue, investigated by means of surface electromyography. Sixty swimmers were recruited, aged 18.63 ± 3.46 years (median 18 years), 28 men (47%), and 32 women (53%), with 7.03 ± 3.9 years of experience. Results: With VE, performance significantly improved in the swim trial (p < 0.001, effect size (ES) −0.95, large). When breaking the results down into the first half (first (0–100 m) vs. the second half (100–200 m)), the ES was large in the first part (−1.11), indicating an improvement in performance. This worsened, however, in the second part of the trial (ES 0.63). In the multivariate analysis, years of experience were found to be a significant predictor of the change in overall performance (p = 0.011). There was a significant increase in muscle fatigue induced by VE, overall, and during the second half, but not during the first half of the trial. Conclusions: The present study indicates that VE during a middle-distance event (200 m) increases performance most in swimmers with little experience. However, it has a negative impact on fatigue

Multiscale Investigation of the Structural, Electrical and Photoluminescence Properties of MoS2 Obtained by MoO3 Sulfurization

In this paper, we report a multiscale investigation of the compositional, morphological, structural, electrical, and optical emission properties of 2H-MoS2 obtained by sulfurization at 800◦C of very thin MoO3 films (with thickness ranging from ~2.8 nm to ~4.2 nm) on a SiO2/Si substrate. XPS analyses confirmed that the sulfurization was very effective in the reduction of the oxide to MoS2, with only a small percentage of residual MoO3 present in the final film. High-resolution TEM/STEM analyses revealed the formation of few (i.e., 2–3 layers) of MoS2 nearly aligned with the SiO2 surface in the case of the thinnest (~2.8 nm) MoO3 film, whereas multilayers of MoS2 partially standing up with respect to the substrate were observed for the ~4.2 nm one. Such different configurations indicate the prevalence of different mechanisms (i.e., vapour-solid surface reaction or S diffusion within the film) as a function of the thickness. The uniform thickness distribution of the few-layer and multilayer MoS2 was confirmed by Raman mapping. Furthermore, the correlative plot of the characteristic A1g-E2g Raman modes revealed a compressive strain (ε ≈ −0.78 ± 0.18%) and the coexistence of n-and p-type doped areas in the few-layer MoS2 on SiO2, where the p-type doping is probably due to the presence of residual MoO3 . Nanoscale resolution current mapping by C-AFM showed local inhomogeneities in the conductivity of the few-layer MoS2, which are well correlated to the lateral changes in the strain detected by Raman. Finally, characteristic spectroscopic signatures of the defects/disorder in MoS2 films produced by sulfurization were identified by a comparative analysis of Raman and photoluminescence (PL) spectra with CVD grown MoS2 flakes

Atomic resolution interface structure and vertical current injection in highly uniform MoS2MoS_{2} heterojunctions with bulk GaN

The integration of two-dimensional $MoS_{2}$ with $GaN$ recently attracted significant interest for future electronic/optoelectronic applications. However, the reported studies have been mainly carried out using heteroepitaxial $GaN$ templates on sapphire substrates, whereas the growth of $MoS_{2}$ on low-dislocation-density bulk GaN can be strategic for the realization of truly vertical devices. In this paper, we report the growth of ultrathin $MoS_{2}$ films, mostly composed by single-layers ($1L$), onto homoepitaxial $n-GaN$ on $n^{+}$ bulk substrates by sulfurization of a pre-deposited $MoO_{x}$ film. Highly uniform and conformal coverage of the $GaN$ surface was demonstrated by atomic force microscopy, while very low tensile strain (0.05%) and a significant $p^{+}$-type doping ($4.5 \times 10^{12} cm^{-2}$) of $1L-MoS_{2}$ was evaluated by Raman mapping. Atomic resolution structural and compositional analyses by aberration-corrected electron microscopy revealed a nearly-ideal van der Waals interface between $MoS_{2}$ and the $Ga$-terminated $GaN$ crystal, where only the topmost $Ga$ atoms are affected by oxidation. Furthermore, the relevant lattice parameters of the $MoS_{2}/GaN$ heterojunction, such as the van der Waals gap, were measured with high precision. Finally, the vertical current injection across this 2D/3D heterojunction has been investigated by nanoscale current-voltage analyses performed by conductive atomic force microscopy, showing a rectifying behavior with an average turn-on voltage $V_{on}=1.7 V$ under forward bias, consistent with the expected band alignment at the interface between $p^{+}$ doped $1L-MoS_{2}$ and $n-GaN$.Comment: 21 pages, 6 figure

Fulvestrant 500 mg versus anastrozole 1 mg for hormone receptor-positive advanced breast cancer (FALCON): an international, randomised, double-blind, phase 3 trial

Background Aromatase inhibitors are a standard of care for hormone receptor-positive locally advanced or metastatic breast cancer. We investigated whether the selective oestrogen receptor degrader fulvestrant could improve progression-free survival compared with anastrozole in postmenopausal patients who had not received previous endocrine therapy. Methods In this phase 3, randomised, double-blind trial, we recruited eligible patients with histologically confirmed oestrogen receptor-positive or progesterone receptor-positive, or both, locally advanced or metastatic breast cancer from 113 academic hospitals and community centres in 20 countries. Eligible patients were endocrine therapy-naive, with WHO performance status 0–2, and at least one measurable or non-measurable lesion. Patients were randomly assigned (1:1) to fulvestrant (500 mg intramuscular injection; on days 0, 14, 28, then every 28 days thereafter) or anastrozole (1 mg orally daily) using a computer-generated randomisation scheme. The primary endpoint was progression-free survival, determined by Response Evaluation Criteria in Solid Tumors version 1·1, intervention by surgery or radiotherapy because of disease deterioration, or death from any cause, assessed in the intention-to-treat population. Safety outcomes were assessed in all patients who received at least one dose of randomised treatment (including placebo). This trial is registered with ClinicalTrials.gov, number NCT01602380. Findings Between Oct 17, 2012, and July 11, 2014, 524 patients were enrolled to this study. Of these, 462 patients were randomised (230 to receive fulvestrant and 232 to receive anastrozole). Progression-free survival was significantly longer in the fulvestrant group than in the anastrozole group (hazard ratio [HR] 0·797, 95% CI 0·637–0·999, p=0·0486). Median progression-free survival was 16·6 months (95% CI 13·83–20·99) in the fulvestrant group versus 13·8 months (11·99–16·59) in the anastrozole group. The most common adverse events were arthralgia (38 [17%] in the fulvestrant group vs 24 [10%] in the anastrozole group) and hot flushes (26 [11%] in the fulvestrant group vs 24 [10%] in the anastrozole group). 16 (7%) of 228 patients in in the fulvestrant group and 11 (5%) of 232 patients in the anastrozole group discontinued because of adverse events. Interpretation Fulvestrant has superior efficacy and is a preferred treatment option for patients with hormone receptor-positive locally advanced or metastatic breast cancer who have not received previous endocrine therapy compared with a third-generation aromatase inhibitor, a standard of care for first-line treatment of these patients

FALCON: A phase III randomised trial of fulvestrant 500 mg vs. anastrozole for hormone receptor-positive advanced breast cancer

Background: This Phase III, randomised, double-blind, multicentre trial (FALCON; NCT01602380) compared the selective estrogen receptor (ER) degrader (SERD) fulvestrant with anastrozole in patients with ER- and/or progesterone receptor-positive locally advanced or metastatic breast cancer who had not received prior hormonal therapy. Methods: Patients were randomised 1:1 to fulvestrant (500 mg IM on Days 0, 14, 28, then each 28 days) or anastrozole (1 mg daily). The primary endpoint was progression-free survival (PFS), assessed via RECIST 1.1, surgery/radiotherapy for disease worsening, or death. Secondary endpoints were: overall survival (OS); objective response rate (ORR, complete response [CR] or partial response [PR]); duration of response (DoR); expected DoR (EDoR); clinical benefit rate (CBR; CR, PR, or stable disease ≥24 weeks); duration of clinical benefit (DoCB); expected DoCB (EDoCB); health-related quality of life (HRQoL); and safety

Multiscale Investigation of the Structural, Electrical and Photoluminescence Properties of MoS2 Obtained by MoO3 Sulfurization

In this paper, we report a multiscale investigation of the compositional, morphological, structural, electrical, and optical emission properties of 2H-MoS(2) obtained by sulfurization at 800 °C of very thin MoO(3) films (with thickness ranging from ~2.8 nm to ~4.2 nm) on a SiO(2)/Si substrate. XPS analyses confirmed that the sulfurization was very effective in the reduction of the oxide to MoS(2,) with only a small percentage of residual MoO(3) present in the final film. High-resolution TEM/STEM analyses revealed the formation of few (i.e., 2–3 layers) of MoS(2) nearly aligned with the SiO(2) surface in the case of the thinnest (~2.8 nm) MoO(3) film, whereas multilayers of MoS(2) partially standing up with respect to the substrate were observed for the ~4.2 nm one. Such different configurations indicate the prevalence of different mechanisms (i.e., vapour-solid surface reaction or S diffusion within the film) as a function of the thickness. The uniform thickness distribution of the few-layer and multilayer MoS(2) was confirmed by Raman mapping. Furthermore, the correlative plot of the characteristic A(1g)-E(2g) Raman modes revealed a compressive strain (ε ≈ −0.78 ± 0.18%) and the coexistence of n- and p-type doped areas in the few-layer MoS(2) on SiO(2), where the p-type doping is probably due to the presence of residual MoO(3). Nanoscale resolution current mapping by C-AFM showed local inhomogeneities in the conductivity of the few-layer MoS(2), which are well correlated to the lateral changes in the strain detected by Raman. Finally, characteristic spectroscopic signatures of the defects/disorder in MoS(2) films produced by sulfurization were identified by a comparative analysis of Raman and photoluminescence (PL) spectra with CVD grown MoS(2) flakes