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Stability and precision of atomic devices are closely tied to the quality and stability of the internal atmosphere of the atomic vapor cells on which they rely. Such atmosphere can be stabilized by building the cell with low permeation materials such as sapphire, or aluminosilicate glass in microfabricated devices. Recently, we showed that permeation barriers made of Al$_{2}$O$_{3}$ thin-film coatings deposited on standard borosilicate glass could be an alternative for buffer gas pressure stabilization. In this study, we hence investigate how helium permeation is influenced by the thickness, ranging from 5 to 40 nm, of such Al$_{2}$O$_{3}$ thin-films coated by atomic layer deposition. Permeation rates are derived from long-term measurements of the pressure-shifted transition frequency of a coherent population trapping (CPT) atomic clock. From thicknesses of 20 nm onward, a significant enhancement of the cell hermeticity is experienced, corresponding to two orders of magnitude lower helium permeation rate. In addition, we test cesium vapor cells filled with neon as a buffer gas and whose windows are coated with 20 nm of Al$_{2}$O$_{3}$. As for helium, the permeation rate of neon is significantly reduced thanks to alumina coatings, leading to a fractional frequency stability of 4x10$^{-12}$ at 1 day when the cell is used in a CPT clock. These features outperform the typical performances of uncoated Cs-Ne borosilicate cells and highlight the significance of Al$_{2}$O$_{3}$ coatings for buffer gas pressure stabilization., Comment: 6 pages, 4 figures

Atomic devices such as atomic clocks and optically-pumped magnetometers rely on the interrogation of atoms contained in a cell whose inner content has to meet high standards of purity and accuracy. Glass-blowing techniques and craftsmanship have evolved over many decades to achieve such standards in macroscopic vapor cells. With the emergence of chip-scale atomic devices, the need for miniaturization and mass fabrication has led to the adoption of microfabrication techniques to make millimeter-scale vapor cells. However, many shortcomings remain and no process has been able to match the quality and versatility of glass-blown cells. Here, we introduce a novel approach to structure, fill and seal microfabricated vapor cells inspired from the century-old approach of glass-blowing. In particular we demonstrate opening and closing single-use zero-leak microfabricated valves, actuated exclusively by laser, and operating in the same way as the "make-seals" and "break-seals" found in the filling apparatus of traditional cells. Such structures are employed to fill cesium vapor cells at the wafer-level. The make-seal structure consists of a glass membrane that can be locally heated and deflected to seal a microchannel. The break-seal is obtained by breaching a silicon wall between cavities. This new approach allows adapting processes previously restricted to glass-blown cells. It can also be extended to vacuum microelectronics and vacuum-packaging of micro-electro-mechanical systems (MEMS) devices., Comment: 13 pages, 6 figures

We describe a high-performance, compact optical frequency standard based on a microfabricated Rb vapor cell and a low-noise, external cavity diode laser operating on the Rb two-photon transition at 778 nm. The optical standard achieves an instability of 1.8x10$^{-13}$/$\sqrt{\tau}$ for times less than 100 s and a flicker noise floor of 1x10$^{-14}$ out to 6000 s. At long integration times, the instability is limited by variations in optical probe power and the AC Stark shift. The retrace was measured to 5.7x10$^{-13}$ after 30 hours of dormancy. Such a simple, yet high-performance optical standard could be suitable as an accurate realization of the SI meter or, if coupled with an optical frequency comb, as a compact atomic clock comparable to a hydrogen maser., Comment: 5 pages, 5 figures

We show that micro-machined non-evaporable getter pumps (NEGs) can extend the time over which laser cooled atoms canbe produced in a magneto-optical trap (MOT), in the absence of other vacuum pumping mechanisms. In a first study, weincorporate a silicon-glass microfabricated ultra-high vacuum (UHV) cell with silicon etched NEG cavities and alumino-silicateglass (ASG) windows and demonstrate the observation of a repeatedly-loading MOT over a 10 minute period with a single laser-activated NEG. In a second study, the capacity of passive pumping with laser activated NEG materials is further investigated ina borosilicate glass-blown cuvette cell containing five NEG tablets. In this cell, the MOT remained visible for over 4 days withoutany external active pumping system. This MOT observation time exceeds the one obtained in the no-NEG scenario by almostfive orders of magnitude. The cell scalability and potential vacuum longevity made possible with NEG materials may enable inthe future the development of miniaturized cold-atom instruments., Comment: 9 pages, 5 figures

Optical frequency standards, lasers stabilized to atomic or molecular transitions, are widely used in length metrology and laser ranging, provide a backbone for optical communications and lie at the heart of next-generation optical atomic clocks. Here we demonstrate a compact, low-power optical frequency standard based on the Doppler-free, two-photon transition in rubidium-87 at 778 nm implemented on a micro-optics breadboard. The optical standard achieves a fractional frequency stability of 2.9x10$^{-12}$/$\sqrt{\tau}$ for averaging times $\tau$ less than 10$^{3}$ s, has a volume of $\approx$35 cm$^3$ and operates on $\approx$450 mW of electrical power. These results demonstrate a key step towards the development of compact optical clocks and the broad dissemination of SI-traceable wavelength references., Comment: 4 pages, 4 figures

Protection of silver mirror stacks from environmental degradation before launching is crucial for space applications. Hereby, we report a comparative study of the advanced protection of silver mirror stacks for space telescopes provided by SiO2 and Al2O3 coatings in conditions of accelerated aging by sulfidation. The model silver stack samples were deposited by cathodic magnetron sputtering on a reference silica substrate for optical applications and a surface-pretreated SiC substrate. Accelerated aging was performed in dry and more severe wet conditions. Optical micrographic observations, surface and interface analysis by Time-of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and reflectivity measurements were combined to comparatively study the effects of degradation. The results show a lower kinetics of degradation by accelerated aging of the stacks protected by the alumina coating in comparable test conditions., Comment: JOURNAL OF MATERIALS SCIENCE \& TECHNOLOGY, 2020, Advanced Corrosion-Resistant Materials and Emerging Applications

Passivation mechanisms were investigated on (100)-oriented Fe-18Cr-13Ni surfaces with direct transfer between surface preparation and analysis by X-ray photoelectron spectroscopy and scanning tunneling microscopy and electrochemical characterization. Starting from oxide-free surfaces, pre-oxidation at saturation under ultra-low pressure (ULP) oxygen markedly promotes the oxide film Cr(III) enrichment and hinders/delays subsequent iron oxidation in water-containing environment. Exposure to sulfuric acid at open circuit potential causes preferential dissolution of oxidized iron species. Anodic passivation forces oxide film re-growth, Cr(III) dehydroxylation and further enrichment. ULP pre-oxidation promotes Cr(III) hydroxide formation at open circuit potential, compactness of the nanogranular oxide film and corrosion protection.

Electrochemical polarization measurements were combined with surface analysis by Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS), X-Ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM) to study the alterations of the passive film on 316L austenitic stainless steel induced by the presence of chlorides in sulfuric acid electrolyte. The work was performed at a stage of initiation of localized corrosion preceding metastable pitting at the micrometer scale as verified by current transient analysis and AFM. The results show that Cl-ions enter the bilayer structure of the surface oxide already formed in the native oxide-covered initial surface state at concentrations below the detection limit of XPS (< 0.5 at%), mostly in the hydroxide outer layer where Fe(III) and Mo(IV,VI) species are concentrated but barely in the oxide inner layer enriched in Cr(III). Their main effect is to produce a less resistive passive state by poisoning dehydroxylation and further Cr(III) and Mo(IV,VI) enrichments obtained in the absence of chlorides. This detrimental effect can be suppressed by pre-passivation in a Cl-free electrolyte, which blocks the entry of chlorides in the passive film, including in the outer exchange layer, and enables the beneficial aging-induced variations of the composition to take place despite the presence of chlorides in the environment.

The durability of passivable metals and alloys is often limited by the stability of the surface oxide film, the passive film, providing self-protection against corrosion in aggressive environments. Improving this stability requires to develop a deeper understanding of the surface structure and initial surface reactivity at the nanometric or atomic scale. In this work we applied scanning tunneling microscopy to unravel the surface structure of a model stainless steel surface in the metallic state and its local modifications induced by initial reaction in dioxygen gas. The results show a rich and complex structure of the oxide-free surface with reconstructed atomic lattice and self-organized lines of surface vacancies at equilibrium. New insight is brought into the mechanisms of initial oxidation at steps and vacancy injection on terraces leading to Cr-rich oxide nuclei and locally Cr-depleted terraces, impacting the subsequent mechanism of chromium enrichment essential to the stability of the surface oxide., Comment: 17 pages, 3 figures

Time of Flight Secondary Ion Mass Spectroscopy, X-Ray Photoelectron Spectroscopy, in situ Photo-Current Spectroscopy and electrochemical analysis were combined to characterize the physicochemical alterations induced by electrochemical passivation of the surface oxide film providing corrosion resistance to 316L stainless steel. The as-prepared surface is covered by a ~2 nm thick, mixed (Cr(III)-Fe(III)) and bi-layered hydroxylated oxide. The inner layer is highly enriched in Cr(III) and the outer layer less so. Molybdenum is concentrated, mostly as Mo(VI), in the outer layer. Nickel is only present at trace level. These inner and outer layers have band gap values of 3.0 and 2.6-2.7 eV, respectively, and the oxide film would behave as an insulator. Electrochemical passivation in sulfuric acid solution causes the preferential dissolution of Fe(III) resulting in the thickness decrease of the outer layer and its increased enrichment in Cr(III) and Mo(IV-VI). The further Cr(III) enrichment of the inner layer causes loss of photoactivity and improved corrosion protection with the anodic shift of the corrosion potential and the increase of the polarization resistance by a factor of ~4. Aging in the passive state promotes the Cr enrichment in the inner barrier layer of the passive film., Comment: 27 pages, 4 tables, 14 figures

In situ Electro-Chemical Scanning Tunneling Microscopy (ECSTM) and Electron Back-Scatter Diffraction analysis of the same local microstructural region were combined to study the relationships between grain boundary (GB) type and structure and passivation on microcrystalline copper in 0.1 M NaOH aqueous solution. The results show that, for high angle random boundaries, passivation in the Cu(I) oxidation range is characterized by a decrease of the depth of GB edge region due to the formation of a passive film locally thicker than on the adjacent grains and thus to anodic oxidation being locally less efficient since it consumes more copper at the grain boundaries. For sigma3 CSL boundaries, the Cu(I) passivation efficiency was observed to be dependent on the local structure of the boundaries. A transition from more to less efficient passivation was observed for a deviation angle of 0.4-0.5{\deg} of the {111} GB plane with respect to the perfect geometry of an ideal coherent twin boundary. This transition would result from the effect on the local anodic oxidation properties of an increased density of misfit dislocations accommodating the increased deviation of the boundary plane from the exact CSL plane., Comment: 27 pages, 3 figures, 1 table

Doppler-free spectroscopy using two counter-propagating dual-frequency laser beams in alkali vapor cells has been demonstrated recently, providing the detection of high-contrast sign-reversed natural-linewidth sub-Doppler resonances. However, to date, only a qualitative theory based on a simplified $\Lambda$-scheme model has been reported to explain underlying physics of this phenomenon. In this work, we develop a general and extended theoretical model of dual-frequency sub-Doppler spectroscopy (DF SDS) for Cs D1 line. The latter considers the real atomic energy structure, main relaxation processes and various nonlinear effects including optical pumping, optical transition saturation, Zeeman and hyperfine coherent population trapping (CPT) states. This model allows to describe quantitatively the respective contributions of involved physical processes and consequently to estimate main properties (height and linewidth) of detected sub-Doppler resonances. Experimental results performed with a Cs vapor micro-fabricated cell are reported and explained by theoretical predictions. Spatial oscillations of the sub-Doppler resonance amplitude with translation of the reflection mirror are highlighted. Reported results show that DF SDS could be a promising approach for the development of a fully-miniaturized and high-performance optical frequency reference, with applications in various compact quantum devices., Comment: 23 pages, 12 figures

Atomic systems have long provided a useful material platform with unique quantum properties. The efficient light-matter interaction in atomic vapors has led to numerous seminal scientific achievements including accurate and precise metrology and quantum devices. In the last few decades, the field of thin optical elements with miniscule features has been extensively studied demonstrating an unprecedented ability to control photonic degrees of freedom, both linearly and non-linearly, with applications spanning from photography and spatial light modulators to cataract surgery implants. Hybridization of atoms with such thin devices may offer a new material system allowing traditional vapor cells with enhanced functionality. Here, we fabricate and demonstrate chip-scale, quantum diffractive optical elements which map atomic states to the spatial distribution of diffracted light. Two foundational diffractive elements, lamellar gratings and Fresnel lenses, are hybridized with atomic channels containing hot atomic vapors which demonstrate exceptionally strong frequency dependent behaviors. Providing the design tools for chip-scale atomic diffractive optical elements develops a path for a variety of compact thin quantum-optical elements., Comment: 9 Pages, including supplementary

The initiation of intergranular corrosion at various types of grain boundaries (GBs) was studied at the nanometer scale on microcrystalline copper in 1 mM HCl aqueous solution. In situ Electrochemical Scanning Tunneling Microscopy (ECSTM) and Electron Back-Scatter Diffraction analysis of the same local microstructural region were combined using an innovative methodology including micro marking performed with the STM tip. The results demonstrate that electrochemically-induced intergranular dissolution, at the surface termination of GBs, is dependent on the grain boundary character. It is found that random high angle boundaries as well as sigma9 coincidence site lattice (CSL) boundaries are susceptible to nanoscale initiation of intergranular corrosion while for sigma3 CSL boundaries the behavior is dependent on the deviation angle of the GB plane from the exact orientation. For the sigma3 twins, a transition from resistance to susceptibility occurs between 1{\deg} and 1.7{\deg} of deviation as a result of the increase of the density of steps (i.e. misorientation dislocations) in the coincidence boundary plane. The work emphasizes the precision needed in the design of the grain boundary network in applications where intergranular corrosion or its initiation must be controlled at the nanoscale., Comment: 25 pages, 1 Table, 6 Figures

Oxide passive films are a key for the durability of metals and alloys components as well as a central issue in corrosion science and engineering. Herein, we discuss current developments of the nanometer and sub-nanometer scale knowledge of the barrier properties and adsorption properties of passive oxide films brought by recent model experimental and theoretical investigations. The discussed aspects include (i) the chromium enrichment and its homogeneity at the nanoscale in passive films formed on Cr-bearing alloys such as stainless steel, (ii) the corrosion properties of grain boundaries in early intergranular corrosion before penetration and propagation in the grain boundary network, and (iii) the interaction of organic inhibitor molecules with incompletely passivated metallic surfaces. In all three cases, key issues are highlighted and future developments that we consider as most relevant are identified., Comment: Current Opinion in Solid State and Materials Science, Elsevier, final accepted preprint

We report the realization and characterization using coherent population trapping (CPT) spectroscopy of an octadecyltrichlorosilane (OTS)-coated centimeter-scale Cs vapor cell. The dual-structure of the resonance lineshape, with presence of a narrow structure line at the top of a Doppler-broadened structure, is clearly observed. The linewidth of the narrow resonance is compared to the linewidth of an evacuated Cs cell and of a buffer gas Cs cell of similar size. The Cs-OTS adsorption energy is measured to be (0.42 $\pm$ 0.03) eV, leading to a clock frequency shift rate of $2.7\times10^{-9}/$K in fractional unit. A hyperfine population lifetime, $T_1$, and a microwave coherence lifetime, $T_2$, of 1.6 and 0.5 ms are reported, corresponding to about 37 and 12 useful bounces, respectively. Atomic-motion induced Ramsey narrowing of dark resonances is observed in Cs-OTS cells by reducing the optical beam diameter. Ramsey CPT fringes are detected using a pulsed CPT interrogation scheme. Potential applications of the Cs-OTS cell to the development of a vapor cell atomic clock are discussed., Comment: 33 pages, 13 figures