Anti-relaxation Coatings Research Articles

Effect of Preparation Processes on Structural Thermal Stability and Collision Energy Dissipation of Common Antirelaxation Coatings on Quartz Substrates.

Paraffin and octadecyltrichlorosilane (OTS) coatings can alleviate collisions between alkali-metal atoms and cell walls and then prolong the atomic spin-polarization lifetime. The surface structure and collision effects of these antirelaxation coatings, as well as the methods to avoid antirelaxation invalidity, have been the focus of researchers. This study investigated the thermolability of coating surface structure and the collision interactions between alkali metal atoms and coatings, considering the influence of various coating preparation factors, where this collision interaction is indirectly analyzed by measuring the collision energy dissipation between an atomic force microscopy (AFM) probe and the atoms on the coating surface. We found that appropriate evaporation time, carbochain length, and postannealing process can enhance the thermostability of the paraffin coating and eliminate its morphological defects. Furthermore, the OTS/water concentration, the soaking time, and the type of solvent have different levels of influence on the cluster formation and the thermostability of the OTS coatings. Moreover, the antirelaxation performance of coatings has been shown to be characterized by counting the energy dissipated when the AFM probe collides with the antirelaxation coating, replacing the conventional light-atom interaction- based method for measuring the relaxation characteristics, but requiring specific coating preparation factors to be maintained.

Energy dissipation during collision for anti-relaxation coatings in alkali-metal vapor cells

Abstract Anti-relaxation surface coatings can reduce collisions between alkali-metal atoms and cell walls, thereby prolonging the spin-polarization lifetime of alkali-metal atoms. This phenomenon can considerably improve the performance of quantum sensors. Researchers have focused on the surface topography and composition of anti-relaxation coatings in alkali-metal vapor cells and on methods that provide an increase in the relaxation time of alkali metals. We proposed a novel method to characterise the coating performance of alkali-metal cells by directly measuring the energy dissipation during collisions between the anti-relaxation coating surface and atoms in the cell. We found that the interactions between alkali-metal atoms and the anti-relaxation coating resemble elastic collisions, which can be indirectly characterised by the energy dissipation during interactions between an atomic force microscopy tip and atoms. In addition, we confirmed that the energy dissipation between collisions is positively correlated with the relaxation characteristics of alkali metals at various temperatures. This discovery is of great significance as it can be utilised to characterise the anti-relaxation coating performance of alkali-metal cells by directly analysing the energy dissipation of anti-relaxation coatings instead of measuring the relaxation time.

A comprehensive study of the effects of different factors on anti-relaxation properties of octadecyltrichlorosilane-coated rubidium vapor cells

Anti-relaxation coatings play an important role in enhancing the polarization lifetime of polarized alkali-metal atoms. In this study, octadecyltrichlorosilane (OTS) was coated in spherical rubidium vapor cells fabricated using borosilicate glass with two stems as anti-relaxation coatings. An orthogonal experiment method was employed to obtain the optimal conditions. The results showed that OTS concentration is the dominant factor in the number of bounces, followed by the soaking time and molar ratio/(H2O:OTS). The optimal parameters were 6 mM of OTS, 6:1 of molar ratio/(H2O:OTS), and 80 min of soaking time. The number of bounces can be up to 200. Atomic force microscope images showed that the number and coverage ratio of clusters on the anti-relaxation coating fabricated by the optimized parameters are significantly less than the number and coverage ratio of clusters formed by other conditions. This means that the clusters in the coatings significantly affect the anti-relaxation performance. In addition, five OTS-coated cells were fabricated by A3B3C5 combination. However, the variability from cell to cell using the exact same preparation procedure can be up to 43.6%. The variability may be caused by the different aging times of the OTS solution. Because only one beaker of OTS solution was prepared, the OTS solution was pumped into the cells in sequence, not at the same time.

Dynamics of Optical Pumping Processes in Coated Cells Filled with Rb Vapour

A better theoretical understanding of the atom – surface interactions and of the experimental consequences and applications to a reproducible method for the construction of reliable coated absorption cells is the main scope of our research. In this paper we report on the influence of diode laser intensity and of diode frequency scanning rate on the spectrum of the D2 line of Rb atoms, contained in paraffin or PolyDiMethylSiloxane (PDMS) coated glass cells. The anti-relaxation coating of inner walls of the glass cells allows to extend the optical orientation of atoms induced by the light to the entire cell volume and atomic velocity distribution. Moreover, in order to further investigate the role of atoms adsorbed in the anti-relaxation coatings, the D2 line spectra are compared for two cases: without and with illumination of the walls of the cell by an ultraviolet lamp. A theoretical model based on rate equations is introduced in order to analyze the experimental results. The extracted behaviour is a simple method to test the conditions of a coated surface. This finds applications in all cases where timely assessment of an organic coating layer is critical, from vapour spectroscopy to magneto-optical trapping of rare and radioactive species.

Evaluation of alternatives to paraffin for antirelaxation coatings

Paraffin wax is currently used as an antirelaxation coating in alkali metal vapor cells since it prevents spin depolarization of alkali atoms. However, the performance of paraffin decreases rapidly above 80 °C due to degradation; thus, the inability to operate at higher temperatures motivates a search for alternatives. Here, the authors use first-principles density functional theory to study rubidium (Rb) atom interactions with paraffin, along with potential alternative coating materials such as pristine and hydrogenated graphene, molybdenum disulfide, and the hydrogen-terminated silicon (111) surface. The authors’ results are in close agreement with experiments that find an adsorption energy of 0.1 eV for Rb on paraffin. The authors also find that Rb adsorbs strongly on graphene, MoS2, and silicon surfaces, but that Rb has a low adsorption energy on hydrogenated graphene, which may be suitable as an antirelaxation coating. The authors link adsorption behavior to the charge-transfer-induced ionic bonding between Rb and the underlying material. In paraffin and hydrogenated graphene, charge transfer is avoided, leading to low Rb adsorption energies for these materials.

Optical characterization of antirelaxation coatings

Antirelaxation coatings (ARC) are used in optical cells containing alkali metal vapor to reduce the depolarization of alkali atoms after collisions with the cell walls. The long-lived ground state polarization is a basis for development of atomic clocks, magnetometers, quantum memory, slow light experiments, precision measurements of fundamental symmetries etc. In this work, a simple method for measuring the number of collisions of the alkali atoms with the cell walls without atomic spin randomization (Nasyrov et al., Proc. SPIE (2015)) was applied to characterize the AR properties of two PDMS coatings prepared from different solutions in ether (PDMS 2% and PDMS 5%). We observed influence of the light-induced atomic desorption (LIAD) on the AR properties of coatings.

Raman and nuclear magnetic resonance investigation of alkali metal vapor interaction with alkene-based anti-relaxation coating.

The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonance investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene.

Method for determining the quality of an antirelaxation coating in optical cells

A simple method is proposed to determine the quality of antirelaxation coatings of the walls of vacuum optical cells containing alkali metal vapors. The method involves recording the time dependence of the fluorescence intensity of alkali atoms during exposure of the cell by resonant radiation pulses. Theory predicts that to determine the coating quality, it is sufficient to know the fluorescence decay rate and the ratio of the fluorescence intensities at the beginning and end of the pulse laser.

Antirelaxation coatings in coherent spectroscopy: Theoretical investigation and experimental test

We describe a theoretical model, based on a density matrix and the Liouville equation, for the investigation of magneto-optical resonances in alkali-metal atomic vapor, in particular in the case of the electromagnetically induced transparency (EIT) in the presence of antirelaxation coatings. The influence of the coating is parametrized with an empirical coefficient describing its efficiency; the calculations are extended to a broad range of coating quality, contrary to previous works, and to uncoated cells. The model takes into account also different configurations for the EIT formation and different efficiency of optical pumping, as determined by the coating characteristics and the atomic energy structure. The model is validated by investigating the EIT with degenerate Zeeman levels in $^{39}\text{K} {D}_{1}$ and Cs ${D}_{2}$ lines, which exhibit respectively an almost negligible and a relevant impact of hyperfine optical pumping. The results are compared to experimental data, exhibiting good agreement; in particular, for the $^{39}\text{K} {D}_{1}$ line, recent findings are shown here in the case of degenerate and nondegenerate EIT with amplitude-modulated light. Our results demonstrate an effective approach for the investigation of antirelaxation coatings and their contribution in the formation of magneto-optical resonances in alkali-metal atoms, in different regimes and with largely different efficiencies. This sheds new light on well-known but not yet entirely clarified phenomena and their behavior as a function of experimental parameters.

Effects of water concentration in the coating solution on the wall relaxation rate of octadecyltrichlorosilane coated rubidium vapor cells

High quality anti-relaxation surface coatings for atomic vapor cells are essential for the preservation of atomic spin coherence and the enhancement of measurement sensitivity. In this paper, we studied the effects of water concentration in octadecyltrichlorosilane (OTS) coating solution on the relaxation rate and its reproducibility of OTS coated Rubidium vapor cells. We found that appropriate water concentration can improve the anti-relaxation performance of OTS coated cells.

Experimental study of 199Hg spin anti-relaxation coatings

We report on a comparison of spin relaxation rates in a $^{199}$Hg magnetometer using different wall coatings. A compact mercury magnetometer was built for this purpose. Glass cells coated with fluorinated materials show longer spin coherence times than if coated with their hydrogenated homologues. The longest spin relaxation time of the mercury vapor was measured with a fluorinated paraffin wall coating.

Low-temperature indium-bonded alkali vapor cell for chip-scale atomic clocks

A low-temperature sealing technique for micro-fabricated alkali vapor cells for chip-scale atomic clock applications is developed and evaluated. A thin-film indium bonding technique was used for sealing the cells at temperatures of ≤140 °C. These sealing temperatures are much lower than those reported for other approaches, and make the technique highly interesting for future micro-fabricated cells, using anti-relaxation wall coatings. Optical and microwave spectroscopy performed on first indium-bonded cells without wall coatings are used to evaluate the cleanliness of the process as well as a potential leak rate of the cells. Both measurements confirm a stable pressure inside the cell and therefore an excellent hermeticity of the indium bonding. The double-resonance measurements performed over several months show an upper limit for the leak rate of 1.5 × 10−13 mbar·l/s. This is in agreement with additional leak-rate measurements using a membrane deflection method on indium-bonded test structures.

Dwell Time Measurement of Wall Collisions of Spin Polarized Rb Atoms on Antirelaxation Coatings

Methods commonly used in surface science have difficulties in studying surface interaction between spin polarized atoms and anti-relaxation coatings in sealed atomic vapour cells. The average dwell time of atom-wall collisions can provide important information for understanding the atom surface interaction. Here we present a simple method for directly measuring the average dwell time of spin polarized rubidium atoms on coated glass surfaces. The method relies on evanescent-wave induced light shift of the Zeeman resonance of Rb atomic spins, and does not depend on the microscopic details of surface interactions. This is the only reliable method currently available for measuring surface dwell time of spin polarized atoms sealed in vapor cells.

Electromagnetically induced transparency in paraffin-coated vapor cells

Antirelaxation coatings in atomic vapor cells allow ground-state coherent spin states to survive many collisions with the cell walls. This reduction in the ground-state decoherence rate gives rise to ultranarrow-bandwidth features in electromagnetically induced transparency (EIT) spectra, which can form the basis of, for example, long-time scale slow and stored light, sensitive magnetometers, and precise frequency standards. Here we study, both experimentally and theoretically, how Zeeman EIT contrast and width in paraffin-coated rubidium vapor cells are determined by cell and laser-beam geometry, laser intensity, and atomic density. Using a picture of Ramsey pulse sequences, where atoms alternately spend ``bright'' and ``dark'' time intervals inside and outside the laser beam, we explain the behavior of EIT features in coated cells, highlighting their unique characteristics and potential applications.

Investigation of antirelaxation coatings for alkali-metal vapor cells using surface science techniques

Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of antirelaxation surface coatings in order to preserve atomic spin polarization. In particular, paraffin has been used for this purpose for several decades and has been demonstrated to allow an atom to experience up to 10 000 collisions with the walls of its container without depolarizing, but the details of its operation remain poorly understood. We apply modern surface and bulk techniques to the study of paraffin coatings in order to characterize the properties that enable the effective preservation of alkali spin polarization. These methods include Fourier transform infrared spectroscopy, differential scanning calorimetry, atomic force microscopy, near-edge x-ray absorption fine structure spectroscopy, and x-ray photoelectron spectroscopy. We also compare the light-induced atomic desorption yields of several different paraffin materials. Experimental results include the determination that crystallinity of the coating material is unnecessary, and the detection of C[Double Bond]C double bonds present within a particular class of effective paraffin coatings. Further study should lead to the development of more robust paraffin antirelaxation coatings, as well as the design and synthesis of new classes of coating materials.

Enhanced magnetic resonance signal of spin-polarized Rb atoms near surfaces of coated cells

We present a detailed experimental and theoretical study of edge enhancement in optically pumped Rb vapor in coated cylindrical pyrex glass cells. The Zeeman polarization of Rb atoms is produced and probed in the vicinity ($~$${10}^{\ensuremath{-}4}$ cm) of the cell surface by evanescent pump and probe beams. Spin-polarized Rb atoms diffuse throughout the cell in the presence of magnetic field gradients. In the present experiment the edge enhanced signal from the back surface of the cell is suppressed compared to that from the front surface, due to the fact that polarization is probed by the evanescent wave at the front surface only. The observed magnetic resonance line shape is reproduced quantitatively by a theoretical model and yields information about the dwell time and relaxation probability of Rb atoms on Pyrex glass surfaces coated with antirelaxation coatings.

Impedance-type measurements using XPS

An impedance type of measurement using X-ray photoelectron spectroscopy is applied for probing charging/discharging dynamics of a sample containing Rb deposited on a SiO 2/Si substrate containing an octadecyltrichlorosilane (OTS) bilayer coating. The OTS bilayer coatings have possible use as anti-relaxation wall coatings for alkali atom vapor cells in miniaturized instruments such as chip-scale atomic clocks, and/or magnetometers. The measurement consists of the application of bipolar square wave pulses of ±10.0 V amplitude to the sample with varying frequencies in the range of 10 −2 to 10 2 Hz while recording X-ray photoemission data. For a conducting sample this type of measurement twins all the photoemission peaks at −10.0 and +10.0 eV positions at all frequencies with exactly 20.0 eV difference between them. However, for samples amenable to charging, the difference between the twinned peaks is less than 20.0 eV, and gradually decreases at correspondingly lower frequencies. For the sample under consideration here at 0.01 Hz, the twinned O1s and Si2p peaks, representing the SiO 2 substrate, are separated by 18.2 eV, displaying a 1.8 eV charging shift. These positions differ from those of the C1s (18.0 eV) representing the OTS bilayer and the Rb3d peaks (18.1 eV). These results reveal that the Rb is electrically (perhaps also chemically) isolated from the OTS bilayer, which may be correlated with the improved performance of the OTS bilayers as anti-relaxation coatings in these alkali atom magnetometer cells.

Evanescent wave magnetometers with ultrathin (∼100μm) cells

We studied the performance of an evanescent wave magnetometer with a coated cell of adjustable length. The cell length varies from a few millimeters to less than 100μm. Two kinds of antirelaxation coatings are used: octadecyltrichlorosilane (OTS) and dichlorooctamethyltetrasiloxane (Surfasil). Sub-kilohertz linewidth can be achieved for a 100μm thick OTS-coated cell. Magnetometers with coated ultrathin cells have superior performance in inhomogeneous magnetic fields, and can achieve a spatial resolution of better than 25μm.

Microwave transitions and nonlinear magneto-optical rotation in anti-relaxation-coated cells

Using laser optical pumping, widths and frequency shifts are determined for microwave transitions between ground-state hyperfine components of $^{85}$Rb and $^{87}$Rb atoms contained in vapor cells with alkane anti-relaxation coatings. The results are compared with data on Zeeman relaxation obtained in nonlinear magneto-optical rotation (NMOR) experiments, a comparison important for quantitative understanding of spin-relaxation mechanisms in coated cells. By comparing cells manufactured over a forty-year period we demonstrate the long-term stability of coated cells, an important property for atomic clocks and magnetometers.