Stable Color Centers Research Articles

Unveiling sulfur vacancy pairs as bright and stable color centers in monolayer WS2

Color centers, arising from zero-dimensional defects, exploit quantum confinement to access internal electron quantum degrees of freedom, holding potential for quantum technologies. Despite intensive research, the structural origin of many color centers remains elusive. In this study, we employ in-situ cathodoluminescence scanning transmission electron microscopy combined with integrated differential phase contrast imaging to examine how defect configuration in tungsten sulfide determines color-center emission. Using an 80-kV accelerated electron beam, defects were deliberately produced, visualized, excited in situ and characterized in real time in monolayer WS2 within hBN|WS2 | hBN heterostructures at 100 K. These color centers were simultaneously measured by cathodoluminescence microscopy and differentiated by machine learning. Supported by DFT calculations, our results identified a crucial sulfur vacancy configuration organized into featured vacancy pairs, generating stable and bright luminescence at 660 nm. These findings elucidate the atomic-level structure-exciton relationship of color centers, advancing our understanding and quantum applications of defects in 2D materials.

Proton Bragg peak imaging by colour centre radiophotoluminescence in lithium fluoride thin film radiation detectors on silicon

Optically transparent lithium fluoride (LiF) thin films, thermally evaporated on Si(100) substrates, are under investigation as novel radiation detectors based on radiophotoluminescence for imaging of the full Bragg curves of proton beams produced by a linear accelerator for proton therapy under development at ENEA C.R. Frascati. Proton irradiation induces the formation of stable colour centres in LiF, amongst which the broadband light-emitting F2 and F3+ aggregate defects, whose concentrations are locally proportional to the energy deposited in the material. Their spatial distributions in the irradiated LiF thin films and crystals are carefully measured by acquiring the latent two-dimensional visible fluorescence images with an optical microscope under blue lamp excitation. Several LiF films grown on silicon substrate were irradiated in air at increasing proton energies up to 35 MeV with their surface parallel to the particle beam and a cleaved edge perpendicularly facing it; for each sample, the fluorescence image acquired from the top surface side of the film allows to obtain the depth profile of the energy released by protons. Differences in colour centre distributions detected in LiF films with respect to LiF crystals are presented and discussed. Accurate Monte Carlo simulations allow to fully explain their experimental behaviours, paving the way towards using LiF film radiation detectors on silicon for the advanced diagnostics of proton beams at typical particle energies used for proton therapy.

Microscopic Study of Optically Stable Coherent Color Centers in Diamond Generated by High-Temperature Annealing

Single color centers in solid have emerged as promising physical platforms for quantum information science. Creating these centers with excellent quantum properties is a key foundation for further technological developments. In particular, the microscopic understanding of the spin-bath environments is the key to engineer color centers for quantum control. In this work, we propose and demonstrate a distinct high-temperature annealing (HTA) approach for creating high-quality nitrogen vacancy (N-V) centers in implantation-free diamonds. Simultaneously using the created N-V centers as probes for their local environment we verify that no damage is microscopically induced by the HTA. Nearly all single N-V centers created in ultralow-nitrogen-concentration membranes possess stable and Fourier-transform-limited optical spectra. Furthermore, HTA strongly reduces noise sources naturally grown in ensemble samples, and leads to more than threefold improvements of decoherence time and sensitivity. We also verify that the vacancy activation and defect reformation, especially H3 and P1 centers, can explain the reconfiguration between spin baths and color centers. This distinct approach will become a powerful tool in vacancy-based quantum technology.

Cryogenic temperature sensing based on the temperature dependence of color centers in optical fibers.

A cryogenic temperature sensor based on the temperature dependence of stable color centers in a commercial single-mode optical fiber is proposed. The radiation induced attenuation spectra at different temperatures are measured and decomposed by Ge-NBOHC and Ge(X) color centers. The configurational coordinate model is used to explain the temperature properties of the color centers. A series of experiments are conducted to evaluate its performance in the temperature range from 10°C to -196°C, and the results suggest that the temperature sensitivity is ∼0.17 dB/km/°C with a resolution of 0.034°C, and the nonlinearity and repeatability error are ±3.8% and 1.4%, respectively.

Group-III quantum defects in diamond are stable spin-1 color centers

Color centers in diamond have emerged as leading solid-state artificial atoms for a range of quantum technologies, from quantum sensing to quantum networks. Concerted research activities are now underway to identify new color centers that combine stable spin and optical properties of the nitrogen vacancy (NV$^-$) with the spectral stability of the silicon vacancy (SiV$^-$) centers in diamond, with recent research identifying other group IV color centers with superior properties. In this Letter, we investigate a new class of diamond quantum emitters from first principles, the group III color centers, which we show to be thermodynamically stable in a spin-1, electric-field insensitive structure. From ab initio electronic structure methods, we characterize the product Jahn-Teller (pJT) effect present in the excited state manifold of these group III color centers, where we capture symmetry-breaking distortions associated with strong electron-phonon coupling. These predictions can guide experimental identification of group III vacancy centers and their use in applications in quantum information science and technology.

Principle study of the europium vacancy color center in a diamond

First-principles analyses are performed on the diamond europium vacancy (EuV) color center. Three different models indicate that the structure of the EuV color center contains a stable vacancy around the Eu atom. Energy band calculations show that the stable EuV color center has spin polarization and its spin-up energy level structure is highly suitable as a single-photon source. The zero-point transition energy is 1.989 eV (623 nm). The existence of metastable energy levels in the EuV is also predicted. Nitrogen atoms have a negative impact on the electronic structure of the EuV, in comparison to diamond color centers such as NE8 and TiV-N.

Dose response and Bragg curve reconstruction by radiophotoluminescence of color centers in lithium fluoride crystals irradiated with 35 MeV proton beams from 0.5 to 50 Gy

Passive solid-state radiation detectors, based on the radiophotoluminescence of stable color centers in nominally pure lithium fluoride (LiF) crystals, have been used for advanced diagnostics of the segment up to 35 MeV of the TOP-IMPLART proton linear accelerator for protontherapy applications, under development at ENEA Frascati. In LiF, proton beams generate a spatial distribution of F2 and F3+ aggregate color centers, which efficiently emit radiophotoluminescence in the red-green spectral range under optical pumping around 450 nm. LiF crystals were irradiated with 35 MeV nominal energy protons at several doses of interest for protontherapy (from 0.5 to 50 Gy). For the first time is shown here the possibility of measuring the radiophotoluminescence spectra of proton irradiated LiF even at such low doses and how the signal showed a linear behavior with dose with a good signal-to-noise ratio. A Bragg-curve image, stored as color-center distribution in a LiF crystal after a 50 Gy-dose irradiation in a particular geometry, was acquired in a conventional fluorescence microscope. After appropriate image processing, the signal intensity resulted to be proportional to the linear energy transfer along the whole Bragg curve. By best-fitting it with an ad-hoc analytical formula, the depth-dose distribution was reconstructed and the proton beam energy and energy spread were estimated.

Quantum Interference of Electromechanically Stabilized Emitters in Nanophotonic Devices

Photon-mediated coupling between distant matter qubits may enable secure communication over long distances, the implementation of distributed quantum computing schemes, and the exploration of new regimes of many-body quantum dynamics. Nanophotonic devices coupled to solid-state quantum emitters represent a promising approach towards realization of these goals, as they combine strong light-matter interaction and high photon collection efficiencies. However, the scalability of these approaches is limited by the frequency mismatch between solid-state emitters and the instability of their optical transitions. Here we present a nano-electromechanical platform for stabilization and tuning of optical transitions of silicon-vacancy (SiV) color centers in diamond nanophotonic devices by dynamically controlling their strain environments. This strain-based tuning scheme has sufficient range and bandwidth to alleviate the spectral mismatch between individual SiV centers. Using strain, we ensure overlap between color center optical transitions and observe an entangled superradiant state by measuring correlations of photons collected from the diamond waveguide. This platform for tuning spectrally stable color centers in nanophotonic waveguides and resonators constitutes an important step towards a scalable quantum network.

Gamma-rays induced color centers in Pb2+ doped CaF2 crystals

Pure and PbF2 doped CaF2 crystals were obtained in our crystal research laboratory. The influence of PbF2 concentration on the color centers induced by γ-and x-rays irradiation were studied. Two broad absorption bands with maxima peaked at 410 and 730 nm appear in the optical absorption spectra; the spectra are quite similar in band structure for all samples and for the both radiation. Different bands showed different responses to the irradiation and to the long-term recovery. The most stable color centers are (Fi0) and the dimer P-P (Pb+(1)-Pb2+). These absorption bands remain stable even for trace amount of Pb2+ ions, so CaF2:PbF2 is not a good material for applications in which the new optical absorption bands are undesirable.

Effect of gamma irradiation on the color, structure and morphology of nickel-doped polyvinyl alcohol films: Alternative use as dosimeter or irradiation indicator

Nickel-doped poly vinyl alcohol (PVA) films were developed for potential application in industrial sectors like radiation processing. We report in this paper the results of an experimental investigation of 60Co source γ-radiation effect on colorimetric, structural and morphological properties of PVA films doped with 0.5% Ni2+ ions (PVA/Ni2+). The PVA/Ni2+ films were irradiated by different gamma-radiation doses varying from 5 to 100 kGy. Color modification of films were studied using L∗, a∗ and b∗ color space measurements as function of the γ-dose and post-irradiation time. The visual change in all samples was verified by microstructure analysis, Fourier transforms infrared (FTIR) spectroscopy, X-Rays diffraction (XRD) and scanning electron microscopy (SEM). The color space exhibited a linear dose response at a dose ranging from 5 to 50 kGy, and then it reached saturation for higher γ-doses. The calculated color changes (ΔE) show a linear dose response relationship from 9.90 to 115.02 in the dose range from 0 to 50 kGy. It showed also the activation of stable color centers. The variability of the color change did not exceed 3% during 80 h (h) post-irradiation. Furthermore, the microstructure analysis evidenced that the color modification due to the optical activation of nickel-oxide (NiO) color center were obtained by complexing Ni2+ ions in irradiated PVA films. The obtained results inspire the possibility to use PVA films for the control process in industrial radiation facilities in dose range 5–50 kGy.

Visible photoluminescence of aggregate colour centres in lithium fluoride thin films for low-energy proton beam radiation detectors at high doses

Colour centres (CCs) in lithium fluoride (LiF) are well known for application in tuneable lasers and dosimeters. The visible photoluminescence (PL) of radiation-induced, broad-band light-emitting aggregate CCs in LiF crystals and films has been proposed for high spatial resolution X-ray imaging; use of LiF-based detectors has been recently successfully extended to advanced diagnostics of low-energy proton beams. After exposure, transversal dose mapping was obtained on LiF films by acquiring the visible PL image of the irradiated spots in a fluorescence microscope under blue-light pumping.Irradiation of thermally evaporated LiF thin films with a proton beam of 3 MeV nominal energy, produced by a linear accelerator, in the fluence range of 1011–1015 protons/cm2, induces the formation of stable CCs, mainly the primary F centre and the aggregate F2 and F3+ defects. A comparison with irradiations performed at 7 MeV shows that the spectrally integrated PL as a function of the absorbed dose is independent on the selected beam energy, at least as far as typical LiF film thicknesses are concerned. The PL behaviour vs. dose can be described by a linear growth which covers up to three order of magnitude, followed by saturation at high values (> ≈105 Gy). The spectral contributions of F2 and F3+ CCs to the detected PL, in the red and in the green respectively, under laser pumping were carefully analysed in order to investigate behaviour differences of these defects at high doses.

Bragg-curve imaging of 7 MeV protons in a lithium fluoride crystal by fluorescence microscopy of colour centres

A lithium fluoride crystal slab was irradiated in air with a proton beam of nominal 7 MeV energy at a linear accelerator that is under development at ENEA C.R. Frascati. The irradiation generated a spatial distribution of stable colour centres in the crystal that could be detected as a luminescent image under blue-light excitation in a fluorescence microscope. The reconstruction of the whole Bragg curve from the luminescent image is here demonstrated for the first time by taking into account finite proton-energy bandwidth and saturation of defect concentration due to high absorbed dose. The obtained results confirm lithium fluoride detectors based on visible photoluminescence of radiation-induced aggregate colour centres as reliable candidate devices for advanced proton-beam diagnostics.

Lithium fluoride thin film detectors for low-energy proton beam diagnostics by photoluminescence of colour centres

Optically transparent LiF thin films thermally evaporated on glass and Si(100) substrates were used for advanced diagnostics of proton beams of energies from 1.4 to 7 MeV produced by a linear accelerator for protontheraphy under development at ENEA C.R. Frascati. The proton irradiation induces the formation of stable colour centres, among them the aggregate F2 and F3+ optically active defects. After exposure of LiF films grown on glass perpendicularly to the proton beams, their accumulated transversal spatial distributions were carefully measured by reading the latent two-dimensional (2-D) fluorescence images stored in the LiF thin layers by local formation of these broad-band visible light-emitting defects with an optical microscope under blue lamp excitation. Taking advantage from the low thickness of LiF thin films and from the linear behaviour of the integrated F2 and F3+ photoluminescence intensities up to the irradiation fluence of ∼5x1015 p/cm2, placing a cleaved LiF film grown on Si substrate with the cutted edge perpendicular to the proton beam, the 2-D fluorescence image of the film surface could allow to obtain the depth profile of the energy released by protons, which mainly lose their energy at the end of the path.

Investigation of intrinsic and extrinsic defects in solid solution Gd3(Al,Ga)5O12 crystals grown by the Czochralski method

Mixed garnet crystals with nominal stoichiometry Gd3Al2.5Ga2.5O12 undoped, single doped with Sm3+, Ho3+, Er3+ and Yb3+ and co-doped with Ho3+ + Yb3+ and Er3+ + Yb3+ were grown by the Czochralski method. Optical spectra and thermal conductivity of obtained single crystal samples were measured and analyzed. Recorded optical absorption spectra revealed that the intensity and spectral characteristics of color centre absorption in the UV region, close to the UV absorption edge of the host, are affected by the type of incorporated rare earth ions. On the other hand, spectral characteristics of stable color centers induced by an intense UV irradiation of crystals depend weakly on the rare earth admixture. Low temperature optical spectra provided the evidence that Sm3+ ions and Er3+ ions occupy at least two different types of sites in this host but Yb3+ ions seem to be located preferentially in identical sites. Thermal conductivity of the crystals at 300 K, weakly affected by incorporated rare earth ions, is comparable to that reported for ordered gallium gadolinium garnet crystals. At cryogenic temperatures, i.e. below ca 80 K, thermal conductivities of the crystals containing rare earth ions are markedly smaller than that of undoped one, however.

Gamma induced thermoluminescence and color centers study of Dy doped LiF micro-cubes

In this paper, we present the thermoluminescence and optical absorption studies of Dy-doped LiF phosphors. The phosphors were synthesized via co-precipitation method, in which the reactions were carried out at fixed pH value 8.00. X-ray diffraction (XRD) patterns revealed single phase structure of phosphors up to concentration (0.04mol%) of Dy in the host lattice of LiF. The field emission scanning electron microscope (FE-SEM) images showed micro-cubical morphologies. The incorporation of Dy in LiF was confirmed from the results of electron dispersive spectroscopy (EDS) and XRD. The thermoluminescence (TL) glow curves of γ-irradiated samples in the dose range (0.1–50kGy) revealed a main dosimetric glow peak positioned at 417K. Moreover, at irradiation dose of 10kGy and above, a broad TL band towards higher temperature side of main dosimetric peak also appeared. Using TLanal program, the complex TL glow curves were deconvoluted and TL kinetics parameters namely; the activation energies, frequency factors and order of kinetics were evaluated. The results revealed the formation of additional localized trapping sites of different values of activation energy and frequency factor in the forbidden band. The optical absorption study revealed the formation of radiation induced stable color centers (CCs) at room temperature. The concentrations of CCs were evaluated using Smakula's formula.

Lithium fluoride colour centres-based imaging detectors for proton beam characterization at high doses

Proton beams of 7 MeV energy, produced by a linear accelerator, were used to irradiate LiF crystals and thin films thermally evaporated on glass substrates in the dose range from 103 to 4 × 106 Gy, inducing the formation of stable photoluminescent colour centres (mainly F2 and F3+), emitting in the visible spectral range. Using a conventional fluorescence microscope, the transversal proton beam intensity was mapped by acquiring the photoluminescence image of the irradiated spots. Image analysis allowed measuring the integrated photoluminescence intensity as a function of the irradiation dose: a linear optical response was obtained up to different maximum dose values, after which a quenching was observed, depending on the nature of the samples (crystals or films). The colour centres formation was investigated by optical absorption spectroscopy at room temperature and the Principal Component Analysis was applied to the absorption spectra of irradiated LiF crystals. In samples irradiated at highest doses, it allowed clearly identifying the formation of more complex aggregate defects, which appears strictly related to the observed photoluminescence quenching effect.

Stable Color Centers Induced in Pure and Neodymium Doped Ca0.28Ba0.72Nb2O6Crystals by Gamma Irradiation

Stable Color Centers Induced in Pure and Neodymium Doped Ca_0.28Ba_0.72Nb₂O₆Crystals by Gamma Irradiation

Solid state detectors based on point defects in lithium fluoride for advanced proton beam diagnostics

Proton beams of 3 and 7MeV energies, produced by a linear accelerator, were used to irradiate lithium fluoride crystals and thermally evaporated LiF thin films in the fluence range of 1011–1015protons/cm2. The irradiation induces the formation of stable colour centres, mainly the primary F centre and the aggregate F2 and F3+ defects. By optical pumping in the blue spectral region, the F2 and F3+ centres emit broad photoluminescence bands in the visible spectral range. By conventional fluorescence microscopy, the integrated photoluminescence intensity was carefully measured in LiF crystals and thin films as a function of the irradiation fluence: a linear optical response was obtained in a large range of fluence, which is dependent on the used LiF samples and the selected beam energy. It was possible to record the transversal proton beam intensity profile by acquiring the photoluminescence image of the irradiated spots on LiF films by a standard optical microscope. Using LiF films grown on silicon substrates irradiated in a particular geometry, the same optical reading microscopy technique allowed one to measure the distribution of colour centres photoluminescence along the depth and direct imaging the Bragg peak position, which gives a rough estimation of the initial proton beam energy.

Molecular-sized fluorescent nanodiamonds

Doping of carbon nanoparticles with impurity atoms is central to their application. However, doping has proven elusive for very small carbon nanoparticles because of their limited availability and a lack of fundamental understanding of impurity stability in such nanostructures. Here, we show that isolated diamond nanoparticles as small as 1.6nm, comprising only ∼400 carbon atoms, are capable of housing stable photoluminescent colour centres, namely the silicon vacancy (SiV). Surprisingly, fluorescence from SiVs is stable over time, and few or only single colour centres are found per nanocrystal. We also observe size-dependent SiV emission supported by quantum-chemical simulation of SiV energy levels in small nanodiamonds. Our work opens the way to investigating the physics and chemistry of molecular-sized cubic carbon clusters and promises the application of ultrasmall non-perturbative fluorescent nanoparticles as markers in microscopy and sensing.

Stability of color centers in LiYF4 crystals at low temperatures

This paper presents the results of examining the stability of induced radiation defects in crystals at 15K. The following regularities have been established. Defects induced at low temperatures in pure and Nd3+ doped LiYF4 crystals are unstable: upon termination of radiation, even at 15K induced color centers are visibly destructed, exposure to the halogen lamp light increases the destruction speed significantly. Heating crystals up to 80K results in complete destruction of color centers induced at 15K.