We investigate the activation yield and optical properties of the negatively charged nitrogen-vacancy (NV (-)) and silicon-vacancy (SiV (-)) centers in single-crystal diamonds, focusing on the effect of proton (p) and carbon-ion (C) irradiation on their formation. The samples, either nitrogen-rich or silicon-implanted, are grown by chemical vapor deposition or high pressure-high temperature synthesis. They are irradiated over three orders of magnitude in fluence, up to similar to 10(14)C/cm(2) or similar to 10(16) p/cm(2), generating up to similar to 10(4) ppm of extra vacancies at the end-of-range. Following thermal annealing at 1150 degrees C for 1 h, we characterize the samples using time-resolved spectroscopy, optical spectroscopy, and optically detected magnetic resonance. The optical properties of the NV (-) and SiV- centers remain stable even at vacancy concentrations of similar to 10(3)-10(4) ppm. At the same time, the activation yield of substitutional nitrogen and (primarily) interstitial silicon increases significantly with vacancy density, from below 2 % to approximately 15-20 % for both centers. A statistical model of defect dynamics during annealing accounts for these results, showing that the activation yield follows a logarithmic dependence on local vacancy concentration-extending over three decades for NV (-) and two for SiV (-).
This paper reports on the instrumentation and expertise developed within the INFN-CHNet network for X-ray and neutron imaging, which enable non-invasive identification of materials and production processes in the field of cultural heritage. INFN-CHNet is the network of the Italian National Institute of Nuclear Physics specifically dedicated to the development and application of scientific methods and technologies to cultural heritage. This article focuses on portable MA-XRF scanners, often complemented by additional techniques, PIXE imaging on a newly developed portable accelerator, X-ray radiography and tomography, exploited to their full potential also through the use of portable systems, and neutron radiography and tomography, which require large-scale facilities. In many respects, the information obtained from X-ray and neutron-based methods is complementary, facilitating a comprehensive characterisation of materials, structures, and manufacturing techniques.
At LABEC (the INFN ion beam laboratory of nuclear techniques for environment and cultural heritage, located in Florence), a novel transportable accelerator for in-situ ion-beam analysis measurements of cultural heritage materials, MACHINA, has been constructed as part of an international collaboration between the INFN and the CERN. Here we present the most recent developments regarding this project, consisting in the design, construction, and testing of the hardware/software of a data acquisition system for prompt photons of characteristic energies emitted following the interaction between charged particles and matter to construct elemental maps, i.e., grayscale digital images showing the spatial distribution of elements in a material of interest wherein the brightness of each individual pixel correlates to the abundance of a given element.
Over the years, transportable instrumentation for cultural heritage (CH) in situ measurements has noticeably widespread, due to logistic, economical and safety reasons. Ion beam analysis, a powerful set of analytical techniques, of great importance for CH, is instead carried out by using fixed instrumentation. To overcome this limit, the Italian national Institute of Nuclear Physics (INFN), CERN (European Centre for Nuclear Research) and the Opificio delle Pietre Dure (OPD), started MACHINA, the “Movable Accelerator for CH In-situ Non-destructive Analysis: the new generation of accelerators for art” to build a transportable accelerator, compact, with strongly reduced weight, absorbed power and cost. MACHINA will be installed at the OPD and dedicated to CH. It will be moved to major conservation centres and museums, when needed. The INFN-CERN proposal, approved in December 2017, became operative in February 2018. 2018 was dedicated to the acquisition of material/instrumentations, to set up both a dummy accelerator (to test the vacuum system) and a vacuum chamber (to test the source). Due to COVID, in 2020 and 2021 the experimental work was slowed down, but we kept developing the control electronics/software and built the second-generation supporting structure. The HF-RFQ power supplies were integrated in October 2021. At the rise of 2022, after conditioning the cavities, we tested the system and in March 2022 we got the first extracted 2-MeV proton beam. In this paper, we present the structure of the MACHINA system, the approach followed and the main solutions adopted, with a special focus on the control system, and finally the first experimental results.
In this paper, NICHE (Neutron Imaging for Cultural HEritage), the new neutron imaging facility of the Italian National Institute of Nuclear Physics (INFN) is shortly presented. We report on the main features of the beamline, the specifications of the detection set-up, and the performances of the imaging system. NICHE is installed at the TRIGA reactor of LENA (Laboratorio Energia Nucleare Applicata) Pavia University laboratory (Italy). The imaging facility was designed during 2020, installed in the spring 2021, and has been in operation since May 2021. NICHE is the first Italian neutron imaging station open to national external users through the INFN-CHNet network application system. NICHE allows users to obtain neutron radiographies and tomographies, thus allowing for morphological characterisation of samples. First results to highlight the potential of the facility are reported. In particular, we show the first results about spatial resolution measurement and 3D reconstruction to provide morphological analysis capabilities.
INFN-CHNet is the cultural heritage network of the Italian National Institute of Nuclear Physics (INFN) and is constituted by units from Italy and from outside Europe, one of them at Universidad Nacional de San Martín (UNSAM) in Buenos Aires, Argentina. As a result of the initiative carried out during 2015 by the Accademia dei Lincei for the year of the Italian culture in Latin America, an INFN-CHNet laboratory was set at CEPyA-UNSAM with the collaboration of INFN and the Restoration Workshop Centro Tarea. Noteworthy, this laboratory is conceived as a multidisciplinary research facility with complementary skills, both scientific and humanistic. In this context, the first instrument jointly set up, optimised, and applied to Cultural Heritage was an X-ray fluorescence scanner. In this manuscript, we describe the instrument and its main features together with a set of representative yet novel applications in the field of cultural heritage, namely, the experimental study of hidden rock art through laboratory replicas that imitates the problems found in the archaeological sites (hematite drawings hidden below carbon deposition); the study and chemical characterisation of archaeological decorated pottery; and finally, the application of the XRF scanner to ancient photography, for quick and accurate identification of materials and techniques employed. Beyond these specific results, the primary output of this initiative has been the conception of a future network of scientific laboratories in South America, coordinated by CEPyA at UNSAM.
Analytical techniques play a fundamental role in heritage science. Among them, Particle Induced X-ray Emission (PIXE) and X-ray Fluorescence (XRF) techniques are widely used in many laboratories for elemental composition analysis. Although they are well-established, a strong effort is put on their upgrade, making them suitable for more and more applications. Over the years, at the INFN-LABEC (the laboratory of nuclear techniques for the environment and cultural heritage of the Italian National Institute of Nuclear Physics), the INFN-CHNet group, the network devoted to cultural heritage, has carried out many technological improvements to the PIXE and XRF set-ups for the analysis of works of art and archaeological finds. Among the many, we recall here the scanning external microbeam facility at the TANDEM accelerator and the MA-XRF scanner. The two instruments have shown complementary features: the former permits quantitative analysis of elements heavier than sodium, which is not possible with the latter in most of the case studies. On the contrary, the scanner has the undeniable advantage of portability, allowing it to work in situ. In this framework of technological developments in heritage science, INFN, CERN, and OPD are jointly carrying on the MACHINA (Movable Accelerator for Cultural Heritage In-situ Non-destructive Analysis) project for on-site Ion Beam Analysis (IBA) studies on cultural heritage.
Using portable instruments for the preservation of artworks in heritage science is more and more common. Among the techniques, Macro X-Ray Fluorescence (MA-XRF) and digital radiography (DR) play a key-role in the field, therefore a number of MA-XRF scanners and radiographic apparatuses have been developed for this scope. Recently, the INFN-CHNet group, the network of the INFN devoted to cultural heritage, has developed a MA-XRF scanner for in-situ analyses. The instrument is fully operative, and it has already been employed in museums, conservation centres and out-door fields. In the present paper, the MA-XRF analysis conducted with the instrument on four Italian artworks undertaking conservation treatments at the conservation centre CCR “La Venaria Reale” are presented. Results on the preliminary test to combine DR with MA-XRF in a single apparatus are also shown.
Silicon-vacancy (SiV) centers in diamond are gaining an increased interest for application, such as in quantum technologies and sensing. Due to the strong luminescence concentrated in its sharp zero-phonon line at room temperature, SiV centers are being investigated as single-photon sources for quantum communication, and also as temperature probes for sensing. Here, we discussed strategies for the fabrication of SiV centers in diamond based on Si-ion implantation followed by thermal activation. SiV color centers in high-quality single crystals have the best optical properties, but polycrystalline micro and nanostructures are interesting for applications in nano-optics. Moreover, we discuss the photoluminescence properties of SiV centers in phosphorous-doped diamond, which are relevant for the creation of electroluminescent devices, and nanophotonics strategies to improve the emission characteristics of the SiV centers. Finally, the optical properties of such centers at room and high temperatures show the robustness of the center and give perspectives for temperature-sensing applications.
In this paper, we have studied an additively manufactured metallic component, intended for ultra-high vacuum application, the exit-snout of the MACHINA transportable proton accelerator beam-line. Metal additive manufacturing components can exhibit heterogeneous and anisotropic microstructures. Two non-destructive imaging techniques, X-ray computed tomography and Neutron Tomography, were employed to examine its microstructure. They unveiled the presence of porosity and channels, the size and composition of grains and intergranular precipitates, and the general behavior of the spatial distribution of the solidification lines. While X-ray computed tomography evidenced qualitative details about the surface roughness and internal defects, neutron tomography showed excellent ability in imaging the spatial density distribution within the component. The anisotropy of the density was attributed to the material building orientation during the 3D printing process. Density variations suggest the possibility of defect pathways, which could affect high vacuum performances. In addition, these results highlight the importance of considering building orientation in the design for additive manufacturing for UHV applications.
Detectors are a key feature of the contemporary scientific approach to cultural heritage (CH), both for diagnostics and conservation. INFN-CHNet is the network of the Italian National Institute of Nuclear Physics that develops and applies new instrumentation for the study of CH. This process results in both optimized traditional state-of-the-art and highly innovative detection setups for spectrometric techniques. Examples of the former are X-rays, gamma-rays, visible-light and particles spectrometers tailored for CH applications, with optimized performances, reliability, weight, transportability, cost, absorbed power, and complementarity with other techniques. Regarding the latter, examples are ARDESIA, the array of detectors at the DAΦNE-Light facility, the MAXRS detection setup at the Riken-RAL muon beamline and the imaging facilities at the LENA Laboratory. Paths for next-generation instruments have been suggested, as in the case of the X-ray Superconductive Detectors and X-ray Microcalorimeter Spectrometers, allowing astonishing improvement in energy resolution. Many issues in CH can now be addressed thanks to scientific techniques exploiting the existing detectors, while many others are still to be addressed and require the development of new approaches and detectors.
The LABEC laboratory, the INFN ion beam laboratory of nuclear techniques for environment and cultural heritage, located in the Scientific and Technological Campus of the University of Florence in Sesto Fiorentino, started its operational activities in 2004, after INFN decided in 2001 to provide our applied nuclear physics group with a large laboratory dedicated to applications of accelerator-related analytical techniques, based on a new 3 MV Tandetron accelerator. The new accelerator greatly improved the performance of existing Ion Beam Analysis (IBA) applications (for which we were using since the 1980s an old single-ended Van de Graaff accelerator) and in addition allowed to start a novel activity of Accelerator Mass Spectrometry (AMS), in particular for 14 C dating. Switching between IBA and AMS operation became very easy and fast, which allowed us high flexibility in programming the activities, mainly focused on studies of cultural heritage and atmospheric aerosol composition, but including also applications to biology, geology, material science and forensics, ion implantation, tests of radiation damage to components, detector performance tests and low-energy nuclear physics. This paper describes the facilities presently available in the LABEC laboratory, their technical features and some success stories of recent applications.
At present, the use of non-destructive, non-invasive X-ray-based techniques is well established in heritage science for the analysis and conservation of works of art. X-ray fluorescence (XRF) plays a fundamental role since it provides information on the elemental composition, contributing to the identification of the materials present on the superficial layers of an artwork. Whenever XRF is combined with the capability of scanning an area to provide the elemental distribution on a surface, the technique is referred to as macro X-ray fluorescence (MA-XRF). The heritage science field, in which the technique is extensively applied, presents a large variety of case studies. Typical examples are paintings, ceramics, metallic objects and manuscripts. This work presents an uncommon application of MA-XRF analysis to furniture. Measurements have been carried out with the MA-XRF scanner of the INFN-CHNet collaboration at the Centro di Conservazione e Restauro “La Venaria Reale”, a leading conservation centre in the field. In particular, a chinoiserie lacquered cabinet of the 18th century and a desk by Pietro Piffetti (1701–1777) have been analysed with a focus on the characterisation of decorative layers and different materials (e.g., gilding in the former and ivory in the latter). The measurements have been carried out using a telemeter for non-planar surfaces, and with collimators of 0.8 mm and 0.4 mm diameter, depending on the spatial resolution needed. The combination of the small measuring head with the use of the telemeter and of a small collimator has guaranteed the ability to scan difficult-to-reach areas with high spatial resolution in a reasonable time (20 × 10 mm2 with 0.2 mm step in less than 20 min).
In the field of Heritage Science, mobile instruments for preservation of artworks are more and more in use. INFN-CHNet, the network of INFN devoted to Cultural Heritage, develops instruments and methods to support the research in the field. Among the others, a MA-XRF scanner was built for in-situ analysis. It is fully operative and has been employed in museums, conservation centres and out-door fields. Recently the INFN-CHNet MA-XRF scanner was employed at the CCR “La Venaria Reale”, Turin, for the analysis of different artworks undertaking conservation treatments. The versatility of the MA-XRF scanner is highlighted by the diversity of the materials and the techniques of the applications (painting on canvas, panel painting, and wooden cabinet).
The line for the pulsed beam of the 3 MeV Tandetron accelerator at LABEC (Florence) has been upgraded for ion implantation experiments aiming at the fabrication of single-photon emitters in a solid-state matrix. A system based on Al attenuators has been calibrated in order to extend the energy range of the implanted ions from MeV down to the tens of keV. A new motorized XY stage has been installed in the implantation chamber for achieving ultra-fine control on the position of each implanted ion, allowing to reach the scale imposed by lateral straggling. A set-up for the activation of the implanted ions has been developed, based on an annealing furnace operating under controlled high-vacuum conditions. The first experiments have been performed with silicon ions implanted in diamond and the luminescent signal of the silicon-vacancy (SiV) center, peaked at 738 nm, has been observed for a wide range of implantation fluences (10(8) + 10(15) cm(-2)) and implantation depths (from a few nm to 2.4 mu m). Studies on the efficiency of the annealing process have been performed and the activation yield has been measured to range from 1% to 3%. The implantation and annealing facility has thus been tuned for the production of SiV centers in diamond, but is in principle suitable for other ion species and solid-state matrices.
Ion irradiation is a widely employed tool to fabricate diamond micro- and nano-structures for applications in integrated photonics and quantum optics. In this context, it is essential to accurately assess the effect of ion-induced damage on the variation of the refractive index of the material, both to control the side effects in the fabrication process and possibly finely tune such variations. Several partially contradictory accounts have been provided on the effect of the ion irradiation on the refractive index of single crystal diamond. These discrepancies may be attributable to the fact that in all cases the ions are implanted in the bulk of the material, thus inducing a series of concurrent effects (volume expansion, stress, doping, etc.). Here we report the systematic characterization of the refractive index variations occurring in a 38 µm thin artificial diamond sample upon irradiation with high-energy (3 MeV and 5 MeV) protons. In this configuration the ions are fully transmitted through the sample, while inducing an almost uniform damage profile with depth. Therefore, our findings conclusively identify and accurately quantify the change in the material polarizability as a function of ion beam damage as the primary cause for the modification of its refractive index.
Despite that the Badakhshan Province (Afghanistan) remains the most plausible hypothesis for the lapis lazuli used in antiquity, alternatives proposed in literature are worth to study to confirm or disprove their historical reliability. In this work, a protocol for determining the provenance of lapis lazuli rocks used for carved artefacts is described. Markers for the univocal attribution of the raw material to a source were identified analysing 45 rocks of known provenance (among which 15 georeferenced) from 4 quarry districts. To the best of our knowledge, this reference database is the widest in provenance studies on lapis lazuli. All the markers are recognisable by means of Ion Beam Analysis (IBA) techniques, in particular micro-proton-induced x-ray emission (PIXE) and micro-ionoluminescence (IL). These techniques are non-invasive and applicable in air, allowing to analyse artworks and rocks of practically any shape and dimension without sample preparation.The protocol was applied to determine the provenance of raw material used for carved lapis lazuli artefacts kept at the Egyptian Museum of Florence, the second most important Egyptian museum in Italy, second only to the museum of Turin. The collection in Florence has a great historical value and includes several lapis lazuli pendants, scarabs, small statuettes and amulets ascribable mainly to the first millennium BC. Following the protocol, 11 of these artefacts were analysed by means of IBA techniques. Results ascribe the raw material to the Afghan quarry district.