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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, through opening and closing single-use zero-leak microfabricated valves. These valves are actuated exclusively by laser, and operate 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., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2022.)

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 1.8×10 -13 τ -1/2 for times less than 100 s and a flicker noise floor of 1×10 -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 5.7×10 -13 after 30 h of dormancy. Such a simple, yet high-performance optical standard could be suitable as an accurate realization of the meter or, if coupled with an optical frequency comb, as a compact atomic clock comparable to a hydrogen maser.

The efficient light-matter interaction and discrete level structure of atomic vapors made possible numerous seminal scientific achievements including time-keeping, extreme non-linear interactions, and strong coupling to electric and magnetic fields in quantum sensors. As such, atomic systems can be regarded as a highly resourceful quantum material platform. Recently, the field of thin optical elements with miniscule features has been extensively studied demonstrating an unprecedented ability to control photonic degrees of freedom. Hybridization of atoms with such thin optical devices may offer a material system enhancing the functionality of traditional vapor cells. Here, we 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 vapors demonstrating exceptionally strong frequency-dependent, non-linear and magneto-optic behaviors. Providing the design tools for chip-scale atomic diffractive optical elements develops a path for compact thin quantum-optical elements.

Atomic level characterization brings fundamental insight into the mechanisms of self-protection against corrosion of metals and alloys by oxide passive films and into how localized corrosion is initiated on passivated metal surfaces. This is illustrated in this overview with selected data obtained at the subnanometre, i.e. atomic or molecular, scale and also at the nanometre scale on single-crystal copper, nickel, chromium and stainless steel surfaces passivated in well-controlled conditions and analysed in situ and/or ex situ by scanning tunnelling microscopy/spectroscopy and atomic force microscopy. A selected example of corrosion modelling by ab initio density functional theory is also presented. The discussed aspects include the surface reconstruction induced by hydroxide adsorption and formation of two-dimensional (hydr)oxide precursors, the atomic structure, orientation and surface hydroxylation of three-dimensional ultrathin oxide passive films, the effect of grain boundaries in polycrystalline passive films acting as preferential sites of passivity breakdown, the differences in local electronic properties measured at grain boundaries of passive films and the role of step edges at the exposed surface of oxide grains on the dissolution of the passive film.This article is part of the themed issue 'The challenges of hydrogen and metals'., (© 2017 The Author(s).)

We report on the metrological characterization of novel commercially available 894.6 nm vertical-cavity surface-emitting lasers (VCSELs), dedicated to Cs D 1 line spectroscopy experiments. The thermal behavior of the VCSELs is reported, highlighting the existence of a minimum threshold current and maximum output power in the 55°C-60°C range. The laser relative intensity noise, measured to be -108  dB/Hz at 10 Hz Fourier frequency f for a laser power of 25 μW, is reduced with increased power. The VCSELs frequency noise is 10 8   Hz 2 /Hz at f=100  Hz. The spectral linewidth of the VCSELs is about 30 MHz. VCSELs injection current can be directly modulated at 4.596 GHz with microwave power in the range of -10 to +0  dBm to generate optical sidebands. A VCSEL was used in a microcell-based Cs atomic clock based on coherent population trapping. A preliminary clock short-term fractional frequency stability of 8×10 -11 τ -1/2 up to about 100 s is reported, demonstrating the suitability of these VCSELs for miniature atomic clock applications.

Porous TiNx Oy -based particles were synthesized by an aerosol spray process. At first, the starting sol solution containing the metal precursor and the nitrogen source is sprayed to form an aerosol that is subsequently pyrolysed at different temperatures. The obtained dried particles are an amorphous coordination "polymer" rich in carbon and nitrogen. These "glassy" particles are finally thermally treated at 800 °C, promoting the crystallization of the particles and the release of a major part of the carbon. As the particles keep their original shape, carbon loss and density increase during the crystallization step and lead to the development of an accessible pore structure. The process was analyzed and extended to the synthesis of other metal nitrides, such as VN and W2 N, thereby showing its general validity for the production of functional nanocrystalline nitride ceramics with high porosity still occupying a relatively small volume, and otherwise not easily accessible., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This paper reports on an original architecture of microfabricated alkali vapor cell designed for miniature atomic clocks. The cell combines diffraction gratings with anisotropically etched single-crystalline silicon sidewalls to route a normally-incident beam in a cavity oriented along the substrate plane. Gratings have been specifically designed to diffract circularly polarized light in the first order, the latter having an angle of diffraction matching the (111) sidewalls orientation. Then, the length of the cavity where light interacts with alkali atoms can be extended. We demonstrate that a longer cell allows to reduce the beam diameter, while preserving the clock performances. As the cavity depth and the beam diameter are reduced, collimation can be performed in a tighter space. This solution relaxes the constraints on the device packaging and is suitable for wafer-level assembly. Several cells have been fabricated and characterized in a clock setup using coherent population trapping spectroscopy. The measured signals exhibit null power linewidths down to 2.23 kHz and high transmission contrasts up to 17%. A high contrast-to-linewidth ratio is found at a linewidth of 4.17 kHz and a contrast of 5.2% in a 7-mm-long cell despite a beam diameter reduced to 600 μm.

The chemical and morphological modifications of FeS thin film as anode material for LiBs have been studied in detail in two classical electrolytes usually used in Li-ion batteries: 1 M LiClO4-PC and 1 M LiPF6-EC/DMC. The X-ray photoelectron spectroscopic (XPS) analysis evidenced the formation of a solid electrolyte interphase (SEI) that contains a more significant amount of inorganic salt residues formed in LiPF6-EC/DMC than in LiClO4-PC, which is likely to increase the ionic resistivity of the SEI, thus impeding the lithiation-delithiation in the first cycles while improving its reversibility. Ion depth profiles performed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) show volume expansion-shrinkage of the thin film leading to cracking and pulverization of the electrode material, which is also confirmed by scanning electron microscopy (SEM) analysis. The prolonged cycling results in penetration and accumulation of the electrolyte in a bulk electrode with accumulation of the inorganic species in the inner part of the SEI enhanced in a fluoride-containing electrolyte. Cycling in these two different electrolytes leads also to formation of two different electrode morphologies: with a compact electrode structure formed in LiClO4-PC and a foam-like, porous structure in LiPF6-EC/DMC. A model of this conversion-type thin film electrode modification based on these thorough spectroscopic and microscopic analyses induced by cycling in two different electrolytes is proposed.

Surface analysis by time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy and scanning tunnelling microscopy has been applied to provide new insight on Mo effects on the composition and nanostructure of the passive films grown in sulfuric acid on well-controlled Fe-17Cr-14.5Ni-2.3Mo(100) austenitic stainless steel single crystal surfaces. A duplex hydroxylated oxide matrix, 1.8-1.9 nm thick, is formed with a strong partition between Cr(iii) and Fe(iii) in the inner and outer layers, respectively. Cr(iii) is increasingly enriched by preferential iron oxide dissolution upon passivation and ageing. Ni, only present as oxide traces in the film, is enriched in the alloy underneath. Mo, mostly present as Mo(iv) in the Cr-rich inner layer prior to anodic polarisation, becomes increasingly enriched (up to 16% of cations) mostly as Mo(vi) in the Fe-rich outer layer of the passive film, with ageing promoting this effect. Metallic Mo is not significantly enriched below the passive film produced from the native oxide covered surface. Mo does not markedly impact the nanogranular morphology of the native oxide film nor its local thickness variations assigned to substrate site effects on Cr(iii) enrichment. Site specific preferential passivation still takes place at the (native) oxide-covered step edges of the alloy surface, and transient dissolution remains preferentially located on the terraces. Nanostructures, possibly Mo-containing, and healing local depressions formed by transient dissolution during passivation, appear as a specific effect of the Mo presence. Another Mo effect, observed even after 20 h of passivation, is to prevent crystallisation at least in the Fe-rich outer part of the passive film where it is concentrated mostly as Mo(vi) (i.e. molybdate) species.

Spectroscopic (XPS, ToF-SIMS) and microscopic (SEM, AFM) analytical methods have been applied to iron oxide (∼Fe2O3) using a thin film approach to bring new insight into the aging mechanisms of conversion-type anode materials for lithium-ion batteries. The results show that repeated lithiation/delithiation causes both chemical and morphological modifications affecting the electrochemical performance. The SEI layer formed by reductive decomposition of the electrolyte remains stable in composition (mostly Li2CO3) but irreversibly thickens upon multicycling. Irreversible swelling of the material accompanied by penetration of the SEI layer and accumulation of non-deconverted material in the bulk of the oxide thin film occurs upon repeated conversion/deconversion. After initial pulverization of the thin film microstructure, grain growth and aggregation are promoted by multicycling. This leads to capacity increase in the first few cycles, but upon further cycling volume expansion and accumulation of non-deconverted material lead to deterioration of the electrode performances.

Atomic layer deposition (ALD) is a thin film deposition technique that is based on alternating and saturating surface reactions of two or more gaseous precursors. The excellent conformality of ALD thin films can be exploited for sealing defects in coatings made by other techniques. Here the corrosion protection properties of hard CrN and diamond-like carbon (DLC) coatings on low alloy steel were improved by ALD sealing with 50 nm thick layers consisting of Al2O3 and Ta2O5 nanolaminates or mixtures. In cross sectional images the ALD layers were found to follow the surface morphology of the CrN coatings uniformly. Furthermore, ALD growth into the pinholes of the CrN coating was verified. In electrochemical measurements the ALD sealing was found to decrease the current density of the CrN coated steel by over 2 orders of magnitude. The neutral salt spray (NSS) durability was also improved: on the best samples the appearance of corrosion spots was delayed from 2 to 168 h. On DLC coatings the adhesion of the ALD sealing layers was weaker, but still clear improvement in NSS durability was achieved indicating sealing of the pinholes.

Oxide layers grown on the surface provide an effective way of protecting metallic materials against corrosion for sustainable use in a broad range of applications. However, the growth of cavities at the metal/oxide interface weakens the adherence of the protective layer and can promote its spallation under service conditions, as observed for alumina layers formed by selective oxidation of aluminide intermetallic alloys used in high-temperature applications. Here we show that direct atomic-scale observations of the interface between an ultrathin protective oxide layer (alumina) grown on an intermetallic titanium aluminide substrate (TiAl) can be performed with techniques sensitive to the topmost atomic layers at the surface. Nanocavities resulting from the self-assembling of atomic vacancies injected at the interface by the growth mechanism of the protective oxide are observed for the first time, bringing new insight into the understanding of the fate of injected cavities in oxidation processes.