Ionic Liquid Ion Sources Research Articles

Model of the meniscus of an ionic-liquid ion source

A simple model of the transfer of charge and ion evaporation in the meniscus of an ionic-liquid ion source working in the purely ionic regime is proposed on the basis of order-of-magnitude estimates which show that, in this regime, (i) the flow in the meniscus is dominated by the viscosity of the liquid and is affected very little by the mass flux accompanying ion evaporation, and (ii) the effect of the space charge around the evaporating surface is negligible and the evaporation current is controlled by the finite electrical conductivity of the liquid. The model predicts that a stationary meniscus of a very polar liquid undergoing ion evaporation is nearly hydrostatic and can exist only below a certain value of the applied electric field, at which the meniscus attains its maximum elongation but stays smooth. The electric current vs applied electric field characteristic displays a frozen regime of negligible ion evaporation at low fields and a conduction-controlled regime at higher fields, with a sharp transition between the two regimes owing to the high sensitivity of the ion evaporation rate to the electric field. A simplified treatment of the flow in the capillary or liquid layer through which liquid is delivered to the meniscus shows that the size of the meniscus decreases and the maximum attainable current increases when the feeding pressure is decreased, and that appropriate combinations of feeding pressure and pressure drop may lead to high maximum currents.

Effect of liquid properties on electrosprays from externally wetted ionic liquid ion sources

Ionic liquid ion sources (ILISs) are externally wetted and electrochemically etched and sharpened tungsten tips used as electrospraying sources for ionic liquids in a vacuum. They have recently shown an ability to operate as emitters of pure ion beams (no drops), even with ionic liquids of moderate surface tension (γ<40dyn∕cm) and electrical conductivity (K<1S∕m) that had in all prior reports (all based on conventional internally fed capillary tips) always operated in the mixed ion-drop regime. The present study uses time of flight mass spectrometry to analyze full ion beams emitted from ILISs for a diversity of ionic liquids with properties in the wide range 0.26<K(S∕m)<2.8, 39.3<γ(dyn∕cm)<48.6. Remarkably, all liquids tested achieve the purely ionic regime. The main effect of reducing electrical conductivity is a reduction of the emission current from 180to10nA.

Monoenergetic source of kilodalton ions from Taylor cones of ionic liquids

The ionic liquid ion sources (ILISs) recently introduced by Lozano and Martinez Sanchez [J. Colloid Interface Sci. 282, 415 (2005)], based on electrochemically etched tungsten tips as emitters for Taylor cones of ionic liquids (ILs), have been tested with ionic liquids [A+B−] of increasing molecular weight and viscosity. These ILs have electrical conductivities well below 1S∕m and were previously thought to be unsuitable to operate in the purely ionic regime because their Taylor cones produce mostly charged drops from conventional capillary tube sources. Strikingly, all the ILs tried on ILIS form charged beams composed exclusively of small ions and cluster ions A+(AB)n or B−(AB)n, with abundances generally peaking at n=1. Particularly interesting are the positive and negative ion beams produced from the room temperature molten salts 1-methyl-3-pentylimidazolium tris(pentafluoroethyl) trifluorophosphate (C5MI–(C2F5)3PF3) and 1-ethyl-3-methylimidazolium bis(pentafluoroethyl) sulfonylimide (EMI–(C2F5SO3)2N). We extend to these heavier species the previous conclusions from Lozano and Martinez Sanchez on the narrow energy distributions of the ion beams. In combination with suitable ILs, this source yields nanoamphere currents of positive and negative monoenergetic molecular ions with masses exceeding 2000amu. Potential applications are in biological secondary ion mass spectrometry, chemically assisted high-resolution ion beam etching, and electrical propulsion. Advantages of the ILISs versus similar liquid metal ion sources include the possibility to form negative as well as positive ion beams and a much wider range of ion compositions and molecular masses.

Energy properties of an EMI-Im ionic liquid ion source

The identity and the energy distributions of positive and negative ions electrostatically extracted from the liquid phase in an ionic liquid ion source (ILIS) are analysed with a time-of-flight mass spectrometer and a multi-grid retarding potential analyzer. Accurate energy measurements using ionic liquids in an externally wetted configuration are reported for the first time. Droplet-free beams are produced using the ionic liquid 1-ethyl-3-methylimidazolium bis(triflouromethylsulfonyl)amide (EMI-Im) in which the solvated ions (EMI-Im)nEMI+ and (EMI-Im)nIm− with n = 0,1,2 are observed. The small ion source size and the energy distribution widths and deficits of a few electronvolts are quite similar to those of liquid metal ion sources, confirming that ILIS can be used in applications requiring highly focusable beams, e.g. sub-micron ion lithography. Measurements also suggest that solvated ions with n ⩾ 1 exhibit post-extraction fragmentation into lighter species at a rate increasing with their original degree of solvation. About 10% of the total beam current is carried away by metastable species that break up almost immediately after extraction while inside the emitter accelerating region.

On the dynamic response of externally wetted ionic liquid ion sources

The electrostatic extraction of nearly monochromatic solvated ions from externally wetted emitters is possible in the case of some ionic liquids or room temperature molten salts. These compact devices are similar to liquid metal ion sources but positive or negative ion beams can be obtained simply by selecting the appropriate polarity for the power supply. dc operation on a single polarity over relatively long periods of time induces electrochemical degradation of the liquid–metal system making voltage alternation at frequencies of the order of 1 Hz necessary to sustain chemical neutrality. This periodic interruption forces a non-steady state behaviour. In particular, the ion current onset is delayed from a square-shaped voltage input signal by a few milliseconds for tungsten metal emitters wetted with the ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate, setting the upper bound for the alternation frequency at about 75 Hz. The dependences of these delays on absolute applied voltages are experimentally explored for this compound, suggesting that viscous drag is the main factor determining the dynamic response.

Ionic liquid ion sources: characterization of externally wetted emitters

The feasibility of electrostatically extracting and accelerating ions from room temperature ionic liquids in a high vacuum environment is investigated using externally wetted emitters similar to those manufactured for liquid metal ion sources, made out of tungsten wire and electrochemically treated to produce a sharp tip and to increase surface wettability. The ionic liquid EMI-BF 4 is used as a prototypical example. The temperature dependence on emission current suggests that liquid flow over the metallic surface is limited by viscosity. Time-of-flight spectrometry indicates that the beam is composed of EMI + and (EMI-BF 4)EMI + ions in the positive polarity and BF 4 − and (EMI-BF 4) BF 4 − ions in the negative polarity, and that these ions are emitted with energies very close to their applied potentials. Angular distribution measurements in positive and negative polarities show that ions travel near the propagation axis, diverging by not more than 18° from the centerline. Thanks to the extraordinary variety of ionic liquids it should be possible to generate a correspondingly large number of bipolar nonmetallic ion beams each with unique properties and applicability in fields as diverse as ion lithography, analytical equipment and space propulsion.

Ionic liquid ion sources: suppression of electrochemical reactions using voltage alternation

The problem of electrochemical decomposition due to extraction of single polarity ions from a novel ionic liquid ion source (ILIS) is solved by periodically alternating the voltage source so that the potential difference that appears across the double layer formed between the emitter conductive material and the liquid is maintained below the electrochemical window limit, thus eliminating electronic reactions. The ionic liquid EMI-BF(4) is used to externally wet a solid tungsten emitter, establishing a physical boundary with a certain liquid-metal contact area. Theoretical and experimental evidence suggests that this area is close to the effective surface involved in the double layer charging dynamics. The extent of this surface is relatively large, thus increasing the net capacitance and consequently the double layer charging time, demonstrating that low frequency voltage alternation of the order of 1 Hz is enough to obtain clean and reliable ion emission.