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A gold surface is functionalized by chemisorption of the enantiopure N,N'-bis-[2,2';5',2â³]tert-thiophene-5-yl methylcyclohexane-1,2-diamine (2T3N), a chiral oligothiophene derivative, via overnight incubation in a 2T3N ethanol solution. The Au|2T3N interface is characterized by x-ray photoelectron circular dichroism and comparing x-ray photoemission spectroscopy and electro-desorption results. Charge transmission at the Au|2T3N| solution interface is characterized by recording the cyclic voltammetry of the Fe(III)/Fe(II) reversible redox couple, finding a charge transfer rate constant, k°, variation from 1 × 10-1 to 3.3 × 10-2 cm s-1, when comparing the bare Au and the Au|2T3N interfaces, respectively. The "anomalous" high value of k° found for the chiral Au|2T3N interface can be rationalized on the basis of the chiral-induced spin selectivity effect, as further proved by magnetic-conductive atomic force microscopy measurements at room temperature. A spin polarization of about 30% is found.
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The relation between morphology and energy level alignment in carbon nanotubes (CNT) is a crucial information for the optimization of applications in nanoelectronics, optics, mechanics and (bio)chemistry. Here we present a study of the relation between the electronic properties and the morphology of single wall CNT (SWCNT), aligned multi wall CNT (MWCNT) and unaligned MWCNT. The CNT were synthesized via catalytic chemical vapor deposition in ultra-high vacuum conditions. Combined ultraviolet photoemission and inverse photoemission (IPES) spectra reveal a high sensitivity to the nanotube morphology. In the case of unaligned SWCNT the distinctive unoccupied Van Hove singularities (vHs) features are observed in the high resolution IPES spectra. Those features are assigned to semiconducting and metallic SWCNT states, according to calculated vHs DOS. The two MWCNT samples are similar in the diameter of the tube (about 15 nm) and present similar filled and empty electronic states, although the measured features in the aligned MWCNT are more defined. Noteworthy, interlayer states are also revealed. Their intensities are directly related to the MWCNT alignment. Focussing and geometrical effects associated to the MWCNT alignment are discussed to account the spectral differences.
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A detailed inverse photoemission study unveils the unoccupied electronic structure induced by the adsorption of CuPc and CoPc phthalocyanines on Au(110) reconstructed channels. The different behavior in the two systems is related to the different intermixing of orbitals with the underlying gold states. Broadening of the density of states at the Fermi level is detected after CoPc adsorption, absent in the case CuPc. A detailed comparison with the element-selective X-ray absorption spectroscopy enlightens and complements the IPES results and confirms a surface-driven intermixing of the CoPc orbitals involved in the interaction, with the out-of-plane Co 3dz2 orbital strongly hybridized with the gold electronic states. Moreover, the contribution of the 3d empty states to the IPES data is reported for FePc, CoPc, and CuPc thin films.
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Objective.Detectors that can provide accurate dosimetry for microbeam radiation therapy (MRT) must possess intrinsic radiation hardness, a high dynamic range, and a micron-scale spatial resolution. In this work we characterize hydrogenated amorphous silicon detectors for MRT dosimetry, presenting a novel combination of flexible, ultra-thin and radiation-hard features.Approach.Two detectors are explored: an n-type/intrinsic/p-type planar diode (NIP) and an NIP with an additional charge selective layer (NIP + CSC).Results.The sensitivity of the NIP + CSC detector was greater than the NIP detector for all measurement conditions. At 1 V and 0 kGy under the 3T Cu-Cu synchrotron broadbeam, the NIP + CSC detector sensitivity of (7.76 ± 0.01) pC cGy-1outperformed the NIP detector sensitivity of (3.55 ± 0.23) pC cGy-1by 219%. The energy dependence of both detectors matches closely to the attenuation coefficient ratio of silicon against water. Radiation damage measurements of both detectors out to 40 kGy revealed a higher radiation tolerance in the NIP detector compared to the NIP + CSC (17.2% and 33.5% degradations, respectively). Percentage depth dose profiles matched the PTW microDiamond detector's performance to within ±6% for all beam filtrations except in 3T Al-Al due to energy dependence. The 3T Cu-Cu microbeam field profile was reconstructed and returned microbeam width and peak-to-peak values of (51 ± 1)µm and (405 ± 5)µm, respectively. The peak-to-valley dose ratio was measured as a function of depth and agrees within error to the values obtained with the PTW microDiamond. X-ray beam induced charge mapping of the detector revealed minimal dose perturbations from extra-cameral materials.Significance.The detectors are comparable to commercially available dosimeters for quality assurance in MRT. With added benefits of being micron-sized and possessing a flexible water-equivalent substrate, these detectors are attractive candidates for quality assurance,in-vivodosimetry and in-line beam monitoring for MRT and FLASH therapy.
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Radiometria , Silício , Silício/química , Radiometria/instrumentação , Hidrogênio , Radioterapia/instrumentaçãoRESUMO
BACKGROUND: The increasing use of complex and high dose-rate treatments in radiation therapy necessitates advanced detectors to provide accurate dosimetry. Rather than relying on pre-treatment quality assurance (QA) measurements alone, many countries are now mandating the use of in vivo dosimetry, whereby a dosimeter is placed on the surface of the patient during treatment. Ideally, in vivo detectors should be flexible to conform to a patient's irregular surfaces. PURPOSE: This study aims to characterize a novel hydrogenated amorphous silicon (a-Si:H) radiation detector for the dosimetry of therapeutic x-ray beams. The detectors are flexible as they are fabricated directly on a flexible polyimide (Kapton) substrate. METHODS: The potential of this technology for application as a real-time flexible detector is investigated through a combined dosimetric and flexibility study. Measurements of fundamental dosimetric quantities were obtained including output factor (OF), dose rate dependence (DPP), energy dependence, percentage depth dose (PDD), and angular dependence. The response of the a-Si:H detectors investigated in this study are benchmarked directly against commercially available ionization chambers and solid-state diodes currently employed for QA practices. RESULTS: The a-Si:H detectors exhibit remarkable dose linearities in the direct detection of kV and MV therapeutic x-rays, with calibrated sensitivities ranging from (0.580 ± 0.002) pC/cGy to (19.36 ± 0.10) pC/cGy as a function of detector thickness, area, and applied bias. Regarding dosimetry, the a-Si:H detectors accurately obtained OF measurements that parallel commercially available detector solutions. The PDD response closely matched the expected profile as predicted via Geant4 simulations, a PTW Farmer ionization chamber and a PTW ROOS chamber. The most significant variation in the PDD performance was 5.67%, observed at a depth of 3 mm for detectors operated unbiased. With an external bias, the discrepancy in PDD response from reference data was confined to ± 2.92% for all depths (surface to 250 mm) in water-equivalent plastic. Very little angular dependence is displayed between irradiations at angles of 0° and 180°, with the most significant variation being a 7.71% decrease in collected charge at a 110° relative angle of incidence. Energy dependence and dose per pulse dependence are also reported, with results in agreement with the literature. Most notably, the flexibility of a-Si:H detectors was quantified for sample bending up to a radius of curvature of 7.98 mm, where the recorded photosensitivity degraded by (-4.9 ± 0.6)% of the initial device response when flat. It is essential to mention that this small bending radius is unlikely during in vivo patient dosimetry. In a more realistic scenario, with a bending radius of 15-20 mm, the variation in detector response remained within ± 4%. After substantial bending, the detector's photosensitivity when returned to a flat condition was (99.1 ± 0.5)% of the original response. CONCLUSIONS: This work successfully characterizes a flexible detector based on thin-film a-Si:H deposited on a Kapton substrate for applications in therapeutic x-ray dosimetry. The detectors exhibit dosimetric performances that parallel commercially available dosimeters, while also demonstrating excellent flexibility results.
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Radiometria , Silício , Radiometria/instrumentação , Hidrogênio , Dosimetria in Vivo , Terapia por Raios X/instrumentação , HumanosRESUMO
Objective. Microbeam radiation therapy (MRT) is an alternative emerging radiotherapy treatment modality which has demonstrated effective radioresistant tumour control while sparing surrounding healthy tissue in preclinical trials. This apparent selectivity is achieved through MRT combining ultra-high dose rates with micron-scale spatial fractionation of the delivered x-ray treatment field. Quality assurance dosimetry for MRT must therefore overcome a significant challenge, as detectors require both a high dynamic range and a high spatial resolution to perform accurately.Approach. In this work, a series of radiation hard a-Si:H diodes, with different thicknesses and carrier selective contact configurations, have been characterised for x-ray dosimetry and real-time beam monitoring applications in extremely high flux beamlines utilised for MRT at the Australian Synchrotron.Results. These devices displayed superior radiation hardness under constant high dose-rate irradiations on the order of 6000 Gy s-1, with a variation in response of 10% over a delivered dose range of approximately 600 kGy. Dose linearity of each detector to x-rays with a peak energy of 117 keV is reported, with sensitivities ranging from (2.74 ± 0.02) nC/Gy to (4.96 ± 0.02) nC/Gy. For detectors with 0.8µm thick active a-Si:H layer, their operation in an edge-on orientation allows for the reconstruction of micron-size beam profiles (microbeams). The microbeams, with a nominal full-width-half-max of 50µm and a peak-to-peak separation of 400µm, were reconstructed with extreme accuracy. The full-width-half-max was observed as 55 ± 1µm. Evaluation of the peak-to-valley dose ratio and dose-rate dependence of the devices, as well as an x-ray induced charge (XBIC) map of a single pixel is also reported.Significance. These devices based on novel a-Si:H technology possess a unique combination of accurate dosimetric performance and radiation resistance, making them an ideal candidate for x-ray dosimetry in high dose-rate environments such as FLASH and MRT.
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Silício , Síncrotrons , Raios X , Austrália , Radiometria/métodosRESUMO
Iron-phthalocyanine molecules deposited on the Au(110) reconstructed channels assemble into one-dimensional molecular chains, whose spatial distribution evolves into different structural phases at increasing molecular density. The plasticity of the Au channels first induces an ordered phase with a 5×5 symmetry, followed by a second long-range ordered structure composed by denser chains with a 5×7 periodicity with respect to the bare Au surface, as observed in the low-energy electron-diffraction (LEED) and grazing incidence X-ray diffraction (GIXRD) patterns. The geometry of the FePc molecular assemblies in the Au nanorails is determined by scanning tunneling microscopy (STM). For the 5×7 phases, the GIXRD analysis identifies a "4-3" rows profile along the [001] direction in the Au surface and an on-top FePc adsorption site, further confirmed by density functional theory (DFT) calculations. The latter also reveals the electronic mixing of the interface states. The chain assembly is driven by the molecule-molecule interaction and the chains interact with the Au nanorails via the central metal atom, while the chain-chain distance in the different structural phases is primarily driven by the plasticity of the Au surface.
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In this paper, by means of high-resolution photoemission, soft X-ray absorption and atomic force microscopy, we investigate, for the first time, the mechanisms of damaging, induced by neutron source, and recovering (after annealing) of p-i-n detector devices based on hydrogenated amorphous silicon (a-Si:H). This investigation will be performed by mean of high-resolution photoemission, soft X-Ray absorption and atomic force microscopy. Due to dangling bonds, the amorphous silicon is a highly defective material. However, by hydrogenation it is possible to reduce the density of the defect by several orders of magnitude, using hydrogenation and this will allow its usage in radiation detector devices. The investigation of the damage induced by exposure to high energy irradiation and its microscopic origin is fundamental since the amount of defects determine the electronic properties of the a-Si:H. The comparison of the spectroscopic results on bare and irradiated samples shows an increased degree of disorder and a strong reduction of the Si-H bonds after irradiation. After annealing we observe a partial recovering of the Si-H bonds, reducing the disorder in the Si (possibly due to the lowering of the radiation-induced dangling bonds). Moreover, effects in the uppermost coating are also observed by spectroscopies.
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A manifestation of electronic entanglement in core-level spectroscopic measurements of diatomic molecules, reported recently by Schöffler and co-workers, is discussed. The results are reminiscent of Schrödinger's famous Gedanken experiment with the cat (see picture).
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Here, we show that the electronic properties of a surface-supported 2-dimensional (2D) layer structure can self-texturize at nanoscale. The local electronic properties are determined by structural relaxation processes through variable adsorption stacking configurations. We demonstrate that the spatially modulated layer-buckling, which arises from the lattice mismatch and the layer/substrate coupling at the GdAu2/Au(111) interface, is sufficient to locally open an energy gap of â¼0.5 eV at the Fermi level in an otherwise metallic layer. Additionally, this out-of-plane displacement of the Gd atoms patterns the character of the hybridized Gd-d states and shifts the center of mass of the Gd 4f multiplet proportionally to the lattice distortion. These findings demonstrate the close correlation between the electronic properties of the 2D-layer and its planarity. We demonstrate that the resulting template shows different chemical reactivities which may find important applications.
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We report on a spectroscopic multitechnique approach to study the metal/radical spinterface formed by a perchlorinated trityl radical derivative and either gold or silver. The spectroscopic fingerprint of their paramagnetic properties could be determined by comparison with their diamagnetic precursor and by DFT calculations. Thanks to the presented approach, we could gain unprecedented insight into the radical-metal interaction and how this latter perturbs the spin polarization and consequently the magnetoelectronic properties of the radical adlayer. Knowledge of the factors influencing the spinterface is an essential tool toward the tailoring of the properties of spin-based electronic devices.
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Metais/química , Percloratos/química , Compostos de Tritil/química , Espectroscopia de Ressonância de Spin EletrônicaRESUMO
A key stage in engineering molecular functional organizations is represented by controlling the supramolecular assembly of single molecular building blocks, tectons, into ordered networks. Here, we show how an open-shell, propeller-like molecule has been deposited under UHV conditions on Au(111) and its supramolecular organization characterized by scanning tunneling microscopy (STM). Racemic islands were observed at room temperature, and their chirality was imaged at the molecular level at low temperature. Modeling further suggests that the observed chirally alternating ordering dominated by intermolecular interactions is energetically favored. Electron paramagnetic resonance and ultraviolet photoemission spectroscopy evidences suggest that the supramolecular networks may preserve the open-shell character of the tecton. These results represent a fundamental step forward toward the engineering of purely organic spintronic devices.
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Understanding the adsorption mechanisms of large molecules on metal surfaces is a demanding task. Theoretical predictions are difficult because of the large number of atoms that have to be considered in the calculations, and experiments aiming to solve the molecule-substrate interaction geometry are almost impossible with standard laboratory techniques. Here, we show that the adsorption of complex organic molecules can induce perfectly ordered nanostructuring of metal surfaces. We use surface X-ray diffraction to investigate in detail the bonding geometry of C(60) with the Pt(111) surface, and to elucidate the interaction mechanism leading to the restructuring of the Pt(111) surface. The chemical interaction between one monolayer of C(60) molecules and the clean Pt(111) surface results in the formation of an ordered sqrt[13] x sqrt[13]R13.9 degrees reconstruction based on the creation of a surface vacancy lattice. The C(60) molecules are located on top of the vacancies, and 12 covalent bonds are formed between the carbon atoms and the 6 platinum surface atoms around the vacancies. In-plane displacements induced on the platinum substrate are of the order of a few picometres in the top layer, and are undetectable in the deeper layers.