Miniature Ion Research Articles

A simplified coaxial ion trap mass analyzer: Characterization of the simplified toroidal ion trap with a rectilinear ion guide

A new miniature coaxial ion trap mass analyzer with a rectilinear ion guide has been constructed using a combination of planar and cylindrical electrodes. The results reported here focus on characterizing the performance of the rectilinear ion guide and simplified toroidal ion trap components. The simplified toroidal ion trap was found to have an ion capacity in excess of 105 ions and mass spectral resolution of 0.5–0.6 when used as a mass analyzer. The ion storage efficiency within the toroidal trapping region was evaluated and found the stored ion population decreased exponentially with storage time. Ion losses depended slightly on the stored βz condition. Ion losses within the toroidal region are attributed primarily to field instabilities at the intersection point of the two components while charge exchange reactions were observed but considered a minor loss mechanism. The ability to mass selectively ejection ions of a specific mass from the toroidal trapping region was characterized and found to approach 100 % efficiency under appropriate ejection conditions.

Kinetic investigation of discharge performance for Xe, Kr, and Ar in a miniature ion thruster using a fast converging PIC-MCC-DSMC model

Abstract The present work develops a full particle-based model that couples the particle-in-cell plus Monte Carlo collision (PIC-MCC) simulation for plasma dynamics and the direct simulation Monte Carlo (DSMC) method for neutral dynamics in a synergistic iterative manner. This new model overcomes the slow convergence issue in the conventional direct coupling approach caused by the disparity of the time scales between the plasma and neutral dynamics. This model is applied to simulate the behavior of xenon (Xe) and its potential alternatives, krypton (Kr) and argon (Ar), in the discharge chamber of a miniature direct current (DC) ion thruster. The results show that a stable discharge is difficult to achieve for Kr and Ar under the operating conditions optimal for Xe. While increasing the discharge voltage can effectively improve the stability of discharge for Kr and Ar, other common strategies such as changing the magnetic field strength, propellant flow rate, and cathode current are not successful. The propellant utilization efficiency and discharge efficiency are affected by both discharge voltage and propellant flow rate. A maximum utilization efficiency and an optimal discharge efficiency are observed for all three propellants, with the values decreasing in the order of Xe, Kr, and Ar. Moreover, the discharge voltage corresponding to the optimal efficiency is inversely proportional to the square root of the propellant mass, indicating that the ion diffusional loss to the wall, rather than the ionization energy, is the dominant factor affecting the discharge performance for alternative propellants in a miniature DC thruster.

Fourier Transform Ion Trap Mass Analysis by Deciphering Ion Ejection Signals in the Frequency Domain.

Mass analysis in an ion trap is conventionally realized through time domain analysis of the ejected ion current collected from an electron multiplier (EM), in which the ion ejection time is found to have a correlation with the mass-to-charge (m/z) ratio of the ion. In this study, we investigated a new method for mass analysis by examining ion ejection signals in the frequency domain. Theoretical analysis and ion trajectory simulations show that ions of the same m/z ratio are ejected from an ion trap at regular intervals, producing a periodic pulsed signal on the EM. The period of this pulsed ejection signal is directly linked to the m/z values of the ions. To realize this method experimentally, a broadband preamplifier was built and integrated on a miniature ion trap mass spectrometer (the "Brick" series from Nier Inc.) to capture this pulsed ion ejection signal collected from the EM. Experimental results were in good agreement with theoretical and simulation analyses. This method has the potential to improve the mass resolution of an ion trap mass analyzer. As a proof-of-concept demonstration, a peak width of 0.1 Da at a m/z value of 281 was achieved in experiments.

A simple numerical simulation model can elucidate the key factors for designing a miniaturized ion trap mass spectrometer

BackgroundMiniature ion trap mass spectrometer enables mass-to-charge ratio analysis of ions via quadrupole field in a low vacuum environment. It plays an important role in on-site detection due to its portability and specificity. In order to gain a deeper understanding of the analysis mechanism of miniature ion trap mass spectrometers, a quadrupole MS ion trajectory numerical simulation model (QITNS) is established in this paper for ions trajectory calculation under the action of quadrupole field, exciting field and neutral gas molecule collision. Compared with the existing methods, the model in this paper is simpler and more direct, which effectively explored the effects of dipole excitation and quadrupole excitation on ion manipulation under high background pressure. ResultsThe simulation results demonstrate that high RF amplitude, low auxiliary AC amplitude and quadrupole excitation can effectively improve the isolation resolution. Besides, it clarified the difference between the analysis mechanism of ion trap mass spectrometers under high background pressure (above 13.332 Pa) and absolute vacuum conditions. The relevant results are consistent with the conclusions of previous experiments and other theories, proving the applicability and accuracy of the proposed calculation model and solution method. SignificanceThis research bears the guiding significance for further understanding the mechanism of quadrupole mass spectrometry as well as designing and developing miniature mass spectrometers.

Ultra-High Vacuum Cells Realized by Miniature Ion Pump Using High-Efficiency Plasma Source.

In recent years, there has been significant interest in quantum technology, characterized by the emergence of quantum computers boasting immense processing power, ultra-sensitive quantum sensors, and ultra-precise atomic clocks. Miniaturization of quantum devices using cold atoms necessitates the employment of an ultra-high vacuum miniature cell with a pressure of approximately 10-6 Pa or even lower. In this study, we developed an ultra-high vacuum cell realized by a miniature ion pump using a high-efficiency plasma source. Initially, an unsealed miniature ion pump was introduced into a vacuum chamber, after which the ion pump's discharge current, depending on vacuum pressures, was evaluated. Subsequently, a miniature vacuum cell was fabricated by hermetically sealing the miniature vacuum pump. The cell was successfully evacuated by a miniature ion pump down to an ultra-high vacuum region, which was derived by the measured discharge current. Our findings demonstrate the feasibility of achieving an ultra-high vacuum cell necessary for the operation of miniature quantum devices.

Research on double resonant excitation in a triangular electrode ion trap with asymmetric geometry.

The triangular electrode linear ion trap with asymmetric geometry has been reported to possess a high ion unidirectional ejection efficiency and a reasonable mass resolution. To further improve its performance, a double resonant excitation method involving a dipolar and a quadrupolar resonant excitation was applied here. The dipolar excitation method was carried out by applying a supplementary alternating voltage out of phase to one pair of the electrodes, whereas the quadrupolar excitation (QE) method was carried out by adding a supplementary alternating voltage in phase to another pair of electrodes. Numerical simulations were performed to explore the impact of the frequency difference between the alternating current (AC) and the QE voltage (∆ω), the frequency of the AC voltage (ωAC), and the QE voltage amplitude (VQE). The mass resolution could be improved to ~4700 , which was approximately twice compared to that with only dipolar resonant excitation, and the ion unidirectional ejection efficiency could be improved to 97%. Even with a high scan rate of 6000 Da/s, there was minimal loss of mass resolution caused by increased scan rate in double resonant excitation mode. By employing the double resonant excitation method, the mass resolution could be further increased while maintaining a considerably high ion unidirectional ejection efficiency, which might be a simple and practical approach for developing a high-performance miniature ion trap mass analyzer.

Influence of the Capillary Design and Conditions upon the Transmission Efficiency of a Portable Ion Trap Mass Spectrometer

The capillary is a widely used atmospheric pressure interface in mass spectrometers that may be heated to enhance the desolvation of ions. In this study, the ion transmission efficiency of a portable ion trap mass spectrometer was investigated using capillaries with different inner diameters and temperatures, different vacuum pressures, and different ion optics designs. Due to the incomplete desolvation and the space charge effect inside the miniature ion funnel, the increase of ion intensities with the inner diameter of the capillary leveled off when the inner diameter of the capillary was larger than 0.37 mm. With the increase of capillary temperature, the ion intensities first increase due to better desolvation and then decrease due to greater diffusion loss. The optimal temperature of the capillary increases with the inner diameter of the capillary and the mass-to-charge ratio of ion. In addition, the pressures of different vacuum stages also exerted remarkable effects on the sensitivity of the portable mass spectrometer. From the perspective of instrument miniaturization, optimal transmission efficiency can be obtained when the first-stage vacuum pressure is maintained from 4 to 6 mbar. For a capillary with an inner diameter of 0.37 mm, the background of mass spectrum can be significantly reduced by replacing the pinhole behind the ion funnel with an off-axis skimmer.

A Miniature Orthogonal Injection Ion Funnel (MO-IF) Providing Enhanced Performance for the Miniature Mass Spectrometer.

The sensitivity of the miniature mass spectrometer (mini-MS) is largely restricted by the ion transmission in rough vacuum region. Even though various "in-line" ion transfer devices have improved mini-MS sensitivity, the severe dynamic gas is still weakening the efficiency of ion transmission in this region. Inspired by the "off-axis" ion funnel design in the lab-scale mass spectrometers, a miniature orthogonal injection ion funnel (MO-IF) was developed in this study for the mini-MS with a continuous atmospheric pressure interface. Capable of directing injected ions by 90° and then transport them forward to the downstream skimmer, the MO-IF enabled the separation of ions from the dynamic gas flow jetted out of the inlet capillary. The key factors were optimized for the MO-IF, including the effects of RF amplitude, DC electric fields, and the position of the repeller. Under optimized conditions, the MO-IF minimized the negative effects of dynamic gas and improved the ion transmission efficiency by ∼2-fold in comparison with the in-line injection ion funnel. As a result, a lower limit of detection of 0.5 ng/mL were obtained with good linearity for hypaconitine. Additionally, the MO-IF further decreased the buffer gas pressure in the second vacuum chamber and improved the mass resolution by 1.1-1.5 times at different scan rates.

Accurate Detection of G-Series Agent Simulants by Pseudo-Multiple Reaction Monitoring on Miniature LIT-MS.

Rapid and accurate on-site detection of chemical warfare agents (CWAs) could defend military and civilian populations against current and emerging chemical weapons. With the development of ambient ionization and linear ion trap technology, the rapid and accurate quantitative determination method of CWAs based on direct ionization and multistage mass spectrometry has attracted widespread attention. In this study, a microliter electrospray ionization-miniature linear ion trap mass spectrometry (LIT-MS) instrument was designed and constructed, and the effects of quadrupole enhanced dipole resonance excitation on the resolution and sensitivity were investigated; consequently, the parameters of CWAs detection were optimized. Based on the broad time-frequency ion excitation technology, accurate multiple reaction monitoring (MRM) quantitative analysis of DMMP (G-series agent simulants, m/z 125 → m/z 93) was obtained. The linear correlation coefficient in the concentration range of 1 to 20 μg/mL could reach 99.02%, and the relative standard deviations (RSD) of continuous repeatability, interday repeatability, and intraday repeatability were all less than 10%. The results showed that the accurate pseudo-MRM detection method based on miniature linear ion trap mass spectrometry for CWAs detection was feasible.

Magnetic field configuration effects on a miniature DC ion thruster with an inverted potential structure

To improve the mass utilization and total efficiency of miniature direct current (DC) ion thrusters, this article proposes a graphene–oxide–semiconductor (GOS) electron source as a cathode in the discharge chamber and neutralizer. To apply the GOS device to the discharge chamber, multiple electron sources were positioned downstream to provide sufficient electrons for plasma generation. Accordingly, the anode was placed upstream of the discharge chamber; thus, the potential structure was inverted from that of a conventional device. Based on this concept, two discharge chamber types were developed with different magnetic field configurations (1- and 2-Cusp types) using a filament cathode and their performance was experimentally evaluated. Probe diagnostics results showed that plasma was generated mainly in the center of the discharge chamber in 1-Cusp, whereas it was generated in the entire discharge chamber in 2-Cusp. Regarding ion beam extraction with 211-hole grids, 1-Cusp exhibited a higher screen current than 2-Cusp. However, using 391-hole grids with an expanded ion-extraction region, 2-Cusp outperformed 1-Cusp with 211-hole grids, attaining a minimum discharge loss of 273 W/A (excluding filament power) and a maximum mass utilization efficiency of 0.48.

Low divergence cold-wall oven for loading ion traps.

We present a compact cold-wall oven that is simple to build and align for loading miniature ion traps with calcium ions. The cold-wall oven, which is a metal-loaded capillary heated only through a portion of its length by the passage of a current, is described and characterized. An atomic beam with a low divergence of 14 mrad is produced. We perform Doppler-sensitive, resonant fluorescence measurements on the atomic beam to characterize the oven's performance. The emission of atoms from the oven is seen within ∼70s after turning on the oven at an electric power consumption of <10 W. The flow rate is measured to be 1.5 ± 0.2 × 109atomss-1 at a temperature of 702 ± 7K. The entire oven assembly is mounted on a CF16 feedthrough. This design can be extended to other species for producing a collimated atomic beam.

Differentiating enantiomers by directional rotation of ions in a mass spectrometer

Conventional mass spectrometry does not distinguish between enantiomers, or mirror-image isomers. Here we report a technique to break the chiral symmetry and to differentiate enantiomers by inducing directional rotation of chiral gas-phase ions. Dual alternating current excitations were applied to manipulate the motions of trapped ions, including the rotation around the center of mass and macro movement around the center of the trap. Differences in collision cross section were induced, which could be measured by ion cloud profiling at high resolutions above 10,000. High-field ion mobility and tandem mass spectrometry analyses of the enantiomers were combined and implemented by using a miniature ion trap mass spectrometer. The effectiveness of the developed method was demonstrated with a variety of organic compounds including amino acids, sugars, and several drug molecules, as well as a proof-of-principle ligand optimization study for asymmetric hydrogenation.

SAM-SFM: High-Efficiency and High-Resolution Tandem Mass Spectrometry Enabled by Sinusoidal Amplitude Modulation of Multiple Sinusoidal Frequency-Modulated Waveforms.

In miniature ion trap mass spectrometry, achieving a balance between isolation resolution and efficiency is a formidable challenge. The presence of absorption curves causes target ions to inadvertently absorb energy from AC signal components near their resonant frequencies. To mitigate this issue, SAM-SFM waveforms introduce a parameter known as the decreasing factor. Unlike SWIFT waveforms, SAM-SFM's spectral profile intentionally departs from a rectangular window, adopting an arch-shaped excitation window to minimize the impact on target ions and improve ion isolation efficiency. SAM-SFM waveforms have the advantage of low computational complexity, enabling real-time computation using an embedded FPGA technology. Regardless of any parameter changes, the FPGA can consistently guarantee waveform output within 1 μs. This not only enhances throughput but also eliminates the need for a PC in miniature mass spectrometry devices. The performance of SAM-SFM has been validated on an improved "Brick" miniature ion trap mass spectrometer. Comparative experiments with SWIFT waveforms confirm the lossless unit-mass isolation capabilities of SAM-SFM. This waveform has the capability to simultaneously isolate multiple target ions, even allowing for the lossless isolation of ions with lower abundance within isotopic clusters, albeit at the cost of requiring extended isolation durations.

Kinetic simulations of low-pressure inductively coupled plasma: an implicit electromagnetic PIC/MCC model with the ADI-FDTD method

Low-pressure inductively coupled plasma (ICP) is promising for space electric propulsion. For the first time, an implicit electromagnetic particle-in-cell Monte Carlo collision model based on the alternating-direction-implicit finite-difference time-domain (ADI-FDTD) method is developed to investigate low-pressure xenon plasma characteristics of a miniature ICP source. The induced simulated electric field is well consistent with that calculated by the finite element method, indicating that this method can provide an accurate estimation of the electromagnetic field. The simulation time step used in the ADI-FDTD method is no longer restricted by the Courant–Friedrichs–Lewy constraints. Compared with the FDTD method, the ADI-FDTD method increases the size of the time step and significantly improves computational efficiency. The method is validated by comparing the simulated and measured electron density and plasma potential profile and reasonable agreement is reached. Therefore, the model is used to investigate the temporal and spatial distribution of plasma properties and the influence of the current amplitude of radio frequency (RF) coil, applied frequency of RF coil and neutral gas pressure on the plasma dynamics in the ionization chamber of a miniature gridded RF ion thruster. To explain the influence of the operating parameters, a concept called ‘the energy relaxation characteristics of electrons in response to the change of electric field’ is proposed and verified. The simulations also find that the oscillation frequency of plasma properties is twice the applied frequency of RF coil. The oscillation characteristics reveal the dynamic energy balance in the ICP. The experiment on the gridded RF ion thruster BHRIT-4 confirms the oscillation by measuring the plasma sheath potential.

Electron extraction mechanism of magnet array microwave discharge neutralizer

Microwave discharge neutralizer is an important part of microwave discharge ion thruster system, which plays a vital role in maintaining potential balance between spacecraft and neutralizing ion beam. Its electron extraction property directly affects the operation condition of ion thruster system. In order to break through the power limit of miniature microwave discharge ion thruster, a magnet array microwave discharge ion thruster system is designed and tested. In the experiment on finalizing magnetic field structure of magnet array microwave discharge neutralizer, an interesting phenomenon is found that the &lt;i&gt;I&lt;/i&gt;-&lt;i&gt;V&lt;/i&gt; curves of electron current, after rotating the magnetic array orientation, are very different. Defining forward direction of magnet array can normally extract electrons, then backward direction of magnet array can hardly extract electrons. Because the diameter of discharge chamber is only 10 mm, it is too small to perform Langmuir probe diagnosis. And thus, an integrative particle-in-cell method is used to simulate the neutralizer operation processes of two different magnetic field structures, and for the sake of accuracy, real vacuum permittivity is used. The simulation results show good consistence with experimental phenomenon. In the initial discharge process, it is found that the magnetic field gradient leads to different plasma distributions; in electron extraction process, it is found that the potential distribution near the orifice determines the electron extraction property of the neutralizer. Through comparing the plasma parameter distributions under different magnetic field structures and operating voltages, an assumption that the ion is an important factor in electron extraction process is proposed. Then, a simulation that ions disappear artificially outside the orifice is conducted, and the simulation results show that electrons cannot be effectively extracted without ions near the orifice. According to the simulation and experiment results, two necessary conditions are summarized for electron extraction of the neutralizer. The first condition is magnetic field structure: the magnetic field gradient should point towards the orifice to guide plasma migration towards the orifice, the second one is potential distribution: there should be enough ions to lift the potential near the orifice for reducing or breaking the potential well. These two conditions can help understand the electron extraction mechanism of microwave discharge neutralizer and provide theoretical reference for optimizing the performance of neutralizer in future.

Effect of Anode Configuration on Ionization Characteristic in Miniature Ion Thrusters

Effect of Anode Configuration on Ionization Characteristic in Miniature Ion Thrusters

SR-Unet: A Super-Resolution Algorithm for Ion Trap Mass Spectrometers Based on the Deep Neural Network.

The mass spectrometer is an important tool for modern chemical analysis and detection. Especially, the emergence of miniature mass spectrometers has provided new tools for field analysis and detection. The resolution of a mass spectrometer reflects the ability of the instrument to discriminate between adjacent mass-to-charge ratio ions, and the higher the resolution, the better the discrimination of complex mixtures. Quadrupole ion traps are generally considered as a low-resolution mass spectrometry method, but they have gained wide attention and development in recent years because of their suitability for miniaturization and high qualitative capability. For an ion trap mass spectrometer, the mass sensitivity and resolution can be mutually constrained and need to be balanced by setting an appropriate scanning speed. In this study, a super-resolution U-net algorithm (SR-Unet) is proposed for ion trap mass spectrometry, which can estimate the possible ions from the overlapping ion peaks of low-resolution spectra and improve the equivalent resolution while ensuring sufficient sensitivity and analysis speed of the instrument. By determining the mass spectra of a linear ion trap mass spectrometer (LTQ XL) in Turbo and Normal scan modes, the same unit mass resolution as that at a scan speed of 16,667 Da/s was successfully obtained at 125,000 Da/s. Also, the experiments demonstrated that the algorithm is capable of the mass-to-charge ratio and instrument migration. SR-Unet can be migrated and applied to a miniature mass spectrometer for cruise detection of volatile organic compounds (VOCs), and the identification of VOC species in Photochemical Assessment Monitoring Stations (PAMS) was improved from 31 to 50 species with the same monitoring and analysis speed requirement. Further, super-unit mass resolution peptide detection was achieved on a miniature mass spectrometer with the help of the SR-Unet algorithm, which reduced the full width at half-maxima (FWHM) of bradykinin divalent ions (m/z 531) from 0.35 to 0.15 Da at a scan speed of 375 Da/s and improved the equivalent resolution to 3540. The proposed method provides a new idea to enhance the field mixture detection capability of miniature ion trap mass spectrometers.

Radial Electric Field Driven Collision-Induced Dissociation in a Miniature Continuous Atmospheric Pressure Interfaced Ion Trap Mass Spectrometer.

Miniature ion trap mass spectrometry with the unique ability of tandem-in-time analysis is extensively used in public security and environmental pollution detection. In this study, a novel radial electric field driven collision-induced dissociation (REFD-CID) is presented with high fragmentation efficiency for different species by adjusting the float DC, the initial kinetic energy of ions, and the pressure in a miniature continuous atmospheric pressure interfaced ion trap mass spectrometer (CAPI-ITMS). It is noteworthy that multiple fragment ions ([M+H-nC2H4]+, where n = 1, 2, 3) of triethyl phosphate were observed with a single injection of ions. The underlying mechanism of the REFD-CID revealed that the enhanced radial electric field by modulation of the float DC drove ions toward regions of intense RF field where broadband heating and dissociation of ions took place through theoretical simulations. Finally, the REFD-CID was utilized to improve the instrument performances. The existence of reagent ions led to a severe space charge effect as the ion injection duration of the CAPI-ITMS was extended to enhance the sensitivity of aniline. Through selective fragmentation of reagent ions, peak broadening and mass shift were eliminated, and meanwhile, a 28-fold improvement of aniline in a signal-to-noise ratio was achieved with the ion injection duration varying from 50 to 2500 ms. Moreover, isomeric illicit drugs (JWH-018 and acetylcodeine) were distinguished by generating multiple characteristic fragment ions, demonstrating potential applications in the identification of synthetic illicit drugs.

Effects of magnetic field configurations on the minimized ECR ion thrusters for micro-Newton and wide-range operations

Space-based gravitational wave detection missions require precise thrusts over a wide-range of 1–100 μN. In this study, the axial ring-cusp magnetic field configuration is used to design a miniature electron cyclotron resonance ion thruster with a radius of 5 mm. Two typical configurations, i.e., open-type and closed-type, are compared in terms of electron density, electron temperature, and thrust for micro-Newton and wide-range operations. The results show that the open-type achieves high performances owing to the high efficiency of absorption of input microwave power. The lower limit of the mass flow rate in the electron cyclotron resonance (ECR) discharge is expanded to a very low value of 3 × 10−2 sccm to achieve 1 μN in the open-type. The thrust in the open-type could be tuned in a wide-range of 1–119 μN, meeting the requirement.

Revealing the plasma confinement behavior of an axial ring cusp hybrid discharge in a miniature ion thruster using PIC/MCC simulation

Micro direct current (DC) ion thrusters have broad application prospects as propulsion systems for micro spacecrafts due to their advantages of high discharge reliability and efficiency. Experiments in the literature show that the plasma discharge under the axial ring cusp hybrid (ARCH) magnetic field has higher discharge efficiency in the discharge chamber of micro DC ion thruster. In this paper, a 2d-3v axisymmetric particle-in-cell/Monte Carlo collision numerical model is developed for the ARCH discharge. This model takes the thermal electron emission including the Schottky effect, various collision processes including the Bohm-type anomalous conductivity and the uneven background gas density distribution in the cathode-anode gap into account. The spatial distributions of plasma characteristics are presented and the advantages of ARCH discharge compared with traditional 3-ring discharge in the discharge chamber of the micro DC ion thruster are analyzed. The longer electron path length and the change of ionization region improve the discharge efficiency in small-scale discharges. Two primary methods for the discharge confinement in the miniature ion thrusters, that is, the magneto-static ‘cusp confinement’ through magnetic cusps and the electrostatic ‘sheath refection confinement’ through the backplate with the lower potential are investigated. The sensitivity of macroscopic current characteristics and microscopic plasma characteristics in the ARCH discharge to the magnetic field strength and backplate biased potential are explored. It is found that there is an optimal magnetic field to maximize the utilization of propellant and minimize the discharge loss. The electrostatic ‘sheath refection confinement’ is conducive to the reduction of discharge loss, however, it is also accompanied by the decline of propellant utilization. The above results provide further support for the design optimization of the micro DC ion thruster discharge chamber.