WO2022008736A1

WO2022008736A1 - Method for producing a beam of charged gas-phase species and associated device

Info

Publication number: WO2022008736A1
Application number: PCT/EP2021/069215
Authority: WO
Inventors: Vincent Huc; Serge Della Negra; Thanh-Loan LAI
Original assignee: Universite Paris-Saclay; Centre National De La Recherche Scientifique
Priority date: 2020-07-10
Filing date: 2021-07-09
Publication date: 2022-01-13
Also published as: FR3112420A1; FR3112420B1; FR3126060A1

Abstract

The invention relates to a method for producing a beam of charged gas-phase species based on a composition comprising at least one polymer and at least one precursor species of the beam. The invention further relates to a device for carrying out the method of the invention.

Description

Method for the production of a beam of charged species in the gaseous phase and associated device

The present invention relates to a process for the production of a beam of charged chemical species in the gas phase. The invention also relates to a device suitable for implementing the method according to the invention.

Prior art

Ion beams in the gas phase are known and find many applications, in particular for the analysis of high-resolution surfaces, for example by SIMS for secondary ion mass spectrometry. These beams are also used for high-resolution imaging or for high-resolution structuring, for example by removal or localized deposition of material, etc.

There are currently three main families of devices allowing the production of ions in the gas phase.

A first type of source, referred to as the “electrospray” type, is based on the ESI technique for electrospray ionization (“electrospray ionization”). This technique is based on the preparation of a dispersion of electrically charged droplets. This first technology meets specific needs in the field of analytical chemistry. For example for mass spectrometry, it makes it possible to obtain intact molecular ions. However, this first technology does not allow the production of stable micrometric ion beams. In particular, the level of focusing of these beams is not sufficient.

A second type of source is based on the SIS technology for "surface ionization" (in English "Surface ionization Source"). The principle of operation of these devices is as follows: a metal or metal alloy surface is heated to high temperature and under reduced pressure in the presence of a material to be ionized introduced in gaseous form. The interaction of the atoms of the material to be ionized with the heated surface leads to their ionization. The ions generated are then extracted from the source and then focused. This technique is particularly suited to the production of beams of alkaline ions (eg: cesium Cs ⁺ ions) and/or alkaline-earth and/or more rarely halogen (eg: iodide I ions). This type of source, however, requires complex heating equipment in order to maintain the chemical species to be ionized in gaseous form. In addition, the choice of the material to be ionized is limited due on the one hand to the need to introduce it in gaseous form and on the other hand to the necessary reactivity. A third type of source is based on the use of conductive liquid materials. Known under the designation LMIS for Liquid Metal Ion Sources (in English “Liquid Metal Ion Sources”), its operating principle is represented in FIG. FIG. 1 represents a device 1 of the LMIS type in which a liquid metal 2 (for example gallium) wets a metal tip 3 brought to a high potential with respect to an extractor 4 placed at a short distance from the metal tip 3. A strong electric field applied to the end 5 of the tip 3 leads to the ionization of the liquid metal. The chemical species 6 thus produced can then be focused and used to impact a target. This type of source is described in particular by Jacques Gierak, Focused Ion Beam Technology and Ultimate Applications, Semiconductor Science and Technology, 24(4):43001, 2009. They are widely used today for surface analysis and structuring at the nanometric scale (FIB probe for Focused Ion Beam). These sources also find numerous applications in the field of microelectronics and are used all over the world. Its operating principle can also be generalized to the use of other conductive liquid materials. Such devices are described in particular in US 6,337,540, US 8,030,621 and US 9,704,685. These ion sources are then designated by the acronym ILIS for ionic liquid ion source (in English “Ionia Liquid Ion Sources”). Another variant uses inorganic salts molten at high temperature (MiLICIS source for microscopic ionic liquid ion source, in English “Microscopie Liquid Ionie Compound Ion Source”). Such devices are in particular described in US 2010/0181493 A1. These technologies based on sources with conductive liquids have many advantages, such as high brilliance (ie. a small emission surface, a narrow velocity distribution of the ions forming the beam and significant focusing) and a long duration of life. These technologies are however limited in the choice of ions that can be generated. Furthermore, the high operating temperatures of the LMIS and MiLICIS sources restrict the choice of ions that can be obtained. Only certain metals, salts or eutectic combinations are accessible by these two methods. The ILIS sources only make it possible to emit ions from a starting compound of the ionic liquid type, which is not always possible. Finally, it is difficult, if not impossible, to prevent the emission, in the ion beam, of droplets of the starting ionic species.

Aims of the invention

There is therefore a need to solve the aforementioned technical problems.

In particular, the present invention aims to solve the technical problem of providing a new process for producing, in a simple manner, beams of a very wide variety of charged species, under conditions as mild as possible, while preventing the formation of charged droplets.

In particular, the present invention aims to solve the technical problem of providing a new method whose implementation makes it possible to generate a beam of complex chemical species, in particular charged nanoparticles.

Summary of the invention

The present invention is based on a process for manufacturing a beam of charged chemical species in gaseous form in which the precursor species of the beam is associated with a polymer, the polymer making it possible to separate the charged species before their extraction/acceleration to form a bundle of charged chemical species in gaseous form.

The method according to the invention makes it possible to solve all the technical problems described above.

The method according to the invention is advantageous in that it allows the preparation of bundles of charged chemical species of varied chemical nature. In particular, it allows the production of beams of monatomic ions, complex charged molecules or even charged nanoparticles.

The method according to the invention is also advantageous in that it is implemented at a reduced temperature, compared to the methods of the prior art. In particular, according to certain embodiments, the method of the invention is effective at ambient temperature.

The process according to the invention is advantageous in that it makes it possible to select with precision the chemical species or species to be extracted, thanks to the specific choice on the one hand of the polymer and on the other hand of the precursor compound used.

The method according to the invention is also advantageous in that it makes it possible to significantly reduce, or even prevent, the emission of droplets of the precursor composition.

The invention relates first of all to a process for the production of a beam of one or more charged chemical species in the gas phase, this process comprising:

1) the supply of a device comprising:

- an emission zone of said beam in contact with a composition comprising at least one polymer and at least one precursor species of the beam, and

- a zone for receiving said beam, 2) optionally, placing the device under vacuum, preferably at a pressure less than or equal to 10 ^-5 hPa, more preferably at a pressure less than or equal to 10 ⁶ hPa, and

3) the production of the beam.

Preferably, the method of the invention comprises:

1) the supply of a device comprising:

- a zone for receiving said beam,

2) the application of a potential difference between the emission zone and the reception zone

3) optionally, placing the device under vacuum, preferably at a pressure less than or equal to 10 ⁵ hPa, more preferably at a pressure less than or equal to 10 ⁶ hPa, and

4) beam production.

The invention also relates to a device suitable for implementing the method according to the invention.

Preferably, the device according to the invention comprises:

- a beam emission zone in contact with a composition comprising at least one polymer and at least one precursor species of a beam of charged chemical species in the gaseous phase,

- a beam reception area, and

- optionally, means making it possible to induce a potential difference between said emission zone and said reception zone.

The invention further relates to the use of a composition comprising at least one polymer and at least one precursor species of a beam of charged chemical species in the gas phase in a device for the production of a beam of charged species in the gas phase, preferably as defined above and in detail below, or in a process for the production of a beam of charged species in the gas phase, preferably as defined above and in a manner detailed below. All of the following paragraphs present variants and preferred embodiments that apply both to the method, to the device and to the use according to the invention as defined above.

According to one embodiment, the method according to the invention comprises, between steps 1) and 2), an intermediate step of applying a potential difference between the emission zone and the reception zone of the beam.

Preferably, the emission zone is heated to a temperature ranging from 15°C to 600°C, preferably from 20°C to 300°C.

According to an advantageous embodiment, the device comprises a reservoir making it possible to contain the composition.

According to a first embodiment, the precursor species of the beam are in the form of a salt, in association with a counter-ion.

Preferably, according to this embodiment, the polymer comprises polar groups in electrostatic interaction with said counterion.

More preferably, the polymer comprises polar groups in dipolar interaction with said counter-ion, advantageously the polar groups of the polymer and said counter-ion are in charge-dipole interaction.

According to a second embodiment, the polymer comprises charged groups and the precursor species of the beam is a counter-ion of said charged groups of the polymer.

Preferably, according to this second embodiment, the charged groups of the polymer are formed by crosslinking of the polymer, preferably by covalent crosslinking of the polymer.

Advantageously, according to this second embodiment, the polymer is chosen from crosslinkable polymers capable of forming charged groups by reaction with a crosslinking agent.

More preferentially, the precursor species of the beam is formed during the crosslinking reaction of the polymer, preferably by decomposition of a crosslinking agent.

According to a first variant, the precursor species of the beam is chosen from: monatomic ions, charged molecules, charged nanoparticles and any one of their mixtures. Preferably, according to this first variant, the precursor species of the beam is chosen from monatomic ions, preferably from cesium Cs ⁺ ions, iodide I ions and any one of their mixtures.

According to a second variant, the precursor species of the beam is chosen from pluriatomic ions, preferably nitrate ions NO ₃ , triiodide ions I ₃ , tribromide ions Br ₃ , perchlorate ions CIO ₄ , azide ions N ₃ and any mixture thereof.

According to a third variant, the precursor species of the beam is chosen from nanoparticles, preferably from metallic nanoparticles, metalloid nanoparticles, carbon nanoparticles, semiconductor nanoparticles and any one of their mixtures.

Detailed description of the invention

The device

The device according to the invention comprises at least one emission zone and at least one zone for receiving the beam of charged chemical species in the gaseous phase.

By “emission zone”, is meant in the sense of the invention the zone of the device in which the beam of charged chemical species in the gaseous phase is produced.

Typically, the emission zone of the device is known per se. Thus, according to one embodiment, the emission zone corresponds to standard equipment conventionally used in devices for the production of ion beams in the gas phase.

In a known manner, the emission zone of the device comprises:

- a first electrode, placed in contact with the precursor composition of the beam,

- a second electrode, also called extractor electrode or extractor, placed opposite the first electrode, and

- Means for inducing a potential difference between said first electrode and said second electrode.

By "electrode" is meant in the sense of the invention an electrically conductive element used to release or capture an electric current.

In the context of the invention, two elements are said to be “in contact” when they are arranged in such a way as to guarantee continuity of potential between these two elements. In particular, the expression “the first electrode is in contact with the precursor composition” means that the potential of the first electrode is transmitted to the whole of the precursor composition.

According to a first embodiment, the first electrode is in direct physical contact with the composition comprising the polymer and the precursor chemical species of the beam.

According to a preferred embodiment, the first electrode is connected to a support element, typically a tip, covered over all or part of its surface with the precursor composition of the beam.

By "support element", is meant in the sense of the invention an element capable of transmitting the electric potential of the first electrode to the precursor composition. The support element is thus intended to be in electrical contact with the first electrode, so that the potential of the first electrode can be transmitted from the first electrode to the precursor composition.

The support element thus differs from the reservoir described below, the function of which is solely to keep the precursor composition in contact with the support element (or directly with the first electrode). Indeed, the reservoir is not intended to transmit the electrical potential of the first electrode to any element and therefore does not form a support within the meaning of the invention. In particular, the reservoir is not in direct electrical contact with the first electrode.

Preferably, according to this preferred embodiment, the first electrode and the precursor composition of the beam are physically separated by said support element.

The support is typically made of an electrically conductive material.

Preferably, the support element is made of a metallic material.

The first electrode and the second electrode are made of an electrically conductive material, preferably of a metallic material.

Preferably, the first electrode is made of a material capable of withstanding temperatures of up to 600°C.

More preferably, the first electrode is made of a material chosen from: gold Au; platinum Pt; tungsten W, optionally coated with a thin layer of gold, and any of their alloys.

Advantageously, the first electrode is made of tungsten W, optionally coated with a thin layer of gold. Preferably, the second electrode (or extractor electrode) is made of a material chosen from among steel, tantalum Ta, molybdenum Mo and any one of their alloys.

Advantageously, the second electrode is in the form of a ring, centered with respect to the end of the first electrode or of the support, in particular of the tip. The end of the first electrode or of the support, in particular of the tip, thus defines the zone of emission of the charged species which then pass through the center of the ring of the extracting electrode to form a beam of charged chemical species.

Means allowing the application of a potential difference between the first electrode and the second electrode consist for example of a high voltage power supply.

Preferably, during operation of the device, the absolute value of the difference between the potential of the first electrode and the second electrode (extraction electrode), also called extraction voltage, ranges from 1 kV to 20 kV, more preferably from 1 kV to 10 kV.

By “reception zone”, is meant in the sense of the invention the zone of the device intended to receive the beam of charged chemical species in the gaseous phase.

Preferably, the reception zone is placed opposite the emission zone, with respect to the generated beam, typically the reception zone comprises a flat surface arranged orthogonally with respect to the generated beam.

According to a preferred embodiment, the reception area further comprises:

- an additional electrode, hereinafter referred to as the third electrode or acceleration electrode, and

- means for inducing a potential difference between the emission zone and said third electrode.

The application of a potential difference between the emission zone and the third electrode makes it possible to fix the energy of the ion beam generated, which makes it possible to focus the generated beam in a specific direction defined by the position of the third electrode.

Preferably, the third electrode is made of an electrically conductive material, preferably it is metallic. More preferably, the third electrode is made of a chemically inert metal, typically chosen for example from (non-exhaustively): silver Ag, platinum Pt, gold Au, tantalum Ta, molybdenum Mo and one any of their alloys.

Advantageously, the third electrode is made of a metal chosen from: tantalum Ta, molybdenum Mo, tungsten W and any one of their alloys, more advantageously from tantalum Ta, molybdenum Mo and any one of their alloys .

Preferably, the surface of the third electrode is planar.

According to an advantageous embodiment, the constituents of the third electrode do not exhibit any interference in X-ray spectroscopy, in particular in energy dispersive X-ray Spectroscopy (EDS) or in photo-electron spectroscopy. XPS (in English “X-ray Photoelectron Spectroscopy”), with the charged species constituting the ion beam, which facilitates its analysis.

Means allowing the application of a potential difference between the emission zone and the third electrode consist for example of a second high voltage power supply.

Preferably, during operation of the device, the absolute value of the difference between the potential of the emission zone and the potential of the third electrode, also called acceleration voltage or ion energy, ranges from 1 kV to 50 kV, more preferably from 1 kV to 30 kV.

Preferably, the device according to the invention also comprises a reservoir making it possible to contain the precursor composition. The presence of a reservoir is necessary to increase the life of the source.

The reservoir is arranged such that the precursor composition is in contact with at least part of the surface of the beam emission zone, preferably with the support element or directly with the first electrode.

The type of reservoir depends on the nature of the precursor composition, and in particular on its viscosity. If the precursor composition has a sufficiently high viscosity to remain on the surface of the emission zone, the material can remain fixed by capillary action and the reservoir can then be placed outside the emission zone. Conversely, if the composition has an insufficiently high viscosity, in particular if it flows under the effect of its own weight and therefore does not remain on the surface of the emission zone, the reservoir must be present at the level of the emission area. Advantageously, the tank is made of a material capable of withstanding temperatures which can range up to 600° C. Examples of such materials are for example glass, ceramic, stainless steel...

According to a first variant, the reservoir is placed close to the emission zone and is equipped with means making it possible to at least partially coat the surface of the emission zone with the composition.

Preferably, according to this variant, the device is equipped with fluidic means, in particular microfluidic means, allowing the transfer of the composition from the reservoir to the surface of the emission zone.

According to a preferred variant, the reservoir is arranged around the emission zone.

According to this preferred variant, the reservoir defines at least one first opening intended to be placed facing the zone for receiving the beam. Thus, the application of a potential difference between the zone of emission and the zone of reception of the beam, leads to the formation at the level of said first opening of the reservoir of a Taylor cone from which the beam of charged cash is issued.

Preferably, according to this variant, the reservoir defines a second opening, said second opening being arranged at the opposite end of the reservoir with respect to the first opening.

Preferably, according to this variant, the reservoir has the shape of a straight cylinder, preferably of circular section, centered around the first electrode. In this case, the first and the second opening are aligned.

Advantageously, the cylinder has a diameter ranging from 50 μm to 5 mm, preferably from 100 μm to 2 mm.

Such a reservoir is also designated by the term “capillary”.

According to one embodiment, the reservoir may have a so-called “L” bent shape. In this case, the reservoir consists of two segments that are substantially perpendicular and interconnected. The end of one of the segments then defines a first opening facing the reception zone of the beam and defining the zone of formation of the Taylor cone. The end of the other segment also defines a second opening arranged perpendicularly with respect to the emission zone.

Thus, and in the event of gas release at the level of the emission zone, the use of a bent-shaped tank makes it possible to evacuate these gas releases, without disturbing the emission zone. Indeed, the gases formed are evacuated through the second opening, thus preventing the migration of the gas towards the emission zone. According to one embodiment, when the reservoir is arranged around the emission zone, the first opening of the reservoir, facing the reception zone of the beam, is equipped with a tip, preferably of frustoconical shape, leaving a passage to the generated beam. The use of a tip then facilitates the formation of the Taylor cone.

Preferably, the tapered tip has an angle substantially equal to 90°.

The tip is typically made of an electrically insulating material, preferably of a rigid material, electrically insulating and chemically inert with respect to the polymer and the precursor species of the beam.

Preferably, the end piece is made of a material capable of withstanding temperatures of up to 600°C.

By way of example of materials suitable for the tip, mention may in particular be made of glass, silicates or even polymeric materials such as polyetheretherketone (PEEK). Also referred to as a sleeve for the tip.

According to a variant, the tip can be machined in the body of the tank, typically when it is first opened.

Optionally, the device of the invention may also comprise means for placing the device under vacuum.

Advantageously, placing the device under vacuum makes it possible to facilitate the emission of charged chemical species in the gaseous phase. The presence of such means is however not mandatory and depends on the nature of the polymer and the precursor species used. Those skilled in the art will determine the need for such means depending on the polymer and the precursor species selected.

Means adapted to the present invention typically make it possible to reach a pressure of less than or equal to 10 ⁵ hPa, preferably less than or equal to 10 ⁶ hPa.

Equipment making it possible to achieve such pressures is well known to those skilled in the art. This equipment can for example consist of the association of a first of the turbo-molecular type or ion pumping making it possible to reach pressures lower than 10 ⁶ hPa and a second so-called primary pump making it possible to reach a limit pressure of 10 ² hPa.

Optionally, the device can also comprise means for heating the composition. By “heating means”, is meant within the meaning of the invention equipment making it possible to bring the composition to a temperature ranging from 15° C. to 600° C., preferably from 20° C. to 300° C.

Advantageously, the presence of heating means makes it possible to facilitate the emission of charged chemical species in the gaseous phase. Their necessity depends both on the nature of the polymer and that of the precursor compound of the beam. Those skilled in the art will determine the need for such means depending on the polymer and the precursor species selected.

The heating means can be direct or indirect.

By “direct heating means”, is meant within the meaning of the invention a heating means arranged in direct physical contact with the composition or the reservoir.

By “indirect heating means”, is meant within the meaning of the invention a heating means physically separated from the composition or from the reservoir by an intermediate material, in particular an insulating material. By way of example, suitable heating means may consist of a metal wire, in particular molybdenum Mo, or tungsten W, wound around the first electrode and/or the reservoir and in which an electric current flows.

The composition

The emission zone of the device is in contact with a precursor composition comprising at least one polymer and at least one precursor species of the beam.

Advantageously, the composition coats all or part of the surface of the first electrode, or of the support, defined above, preferably on its proximal end of the second electrode (extraction electrode).

Preferably, at least 50% of the surface of the first electrode or of the support, in particular of the tip, is coated with the composition, more preferably at least 75%, even more preferably at least 90%, advantageously at least 95%, and more preferably 100%.

Preferably, the precursor species of the beam and the polymer are present in the composition according to a molar ratio ranging from 10:1 to 1:1000, more preferably from 10:1 to 1:500, and even more preferably from 10: 1 to 1: 100.

The composition can also comprise other compounds capable of modifying the properties of the composition. These optional compounds can for example be introduced to modify the viscosity of the composition, its melting point or its adhesion properties, etc. Examples of such optional compounds are, for example, polymers different from the polymer defined below and detailed below, in particular chosen from ionomers.

The composition may also comprise compounds or polymers having oxidation-reduction properties, making it possible to modulate the redox (oxidation-reduction) effects occurring during the production of the beam.

Charged chemical species

The method according to the invention allows the production of a beam comprising one or more gaseous chemical species whose precise chemical nature is predetermined by the choice on the one hand of the precursor species of the beam and on the other hand of the polymer. The choice of the elements constituting the composition makes it possible in particular to control the charge of the chemical elements constituting the beam but also their size, in particular in the context of beams of charged nanoparticles.

Preferably, the charged chemical species or species constituting the beam are chosen from: monatomic ions, charged molecules, charged nanoparticles and any of their mixtures.

When the charged chemical species constituting the beam are chosen from monatomic ions, they are preferably chosen from alkali metal ions, alkaline-earth ions, halide ions, metal ions and any one of their mixtures, from preferably from alkaline ions, halide ions, and any one of their mixtures, more preferably from cesium Cs ⁺ ions, iodide I ions, and any one of their mixtures.

When the charged chemical species constituting the beam are chosen from charged molecules, they are preferably chosen from chemically reactive ions, more preferably from nitrate ions NO ₃ , triiodide ions

I ₃ , Br ₃ tribromide ions, CIO ₄ perchlorate ions, N ₃ azide ions and any one of their mixtures.

Among the charged molecules capable of forming the beam of the invention, mention may also be made of tosylate ions.

When the charged chemical species constituting the beam are chosen from charged nanoparticles, they are preferably chosen from metallic nanoparticles; metalloid nanoparticles; carbonaceous, hydrogenated or non-hydrogenated nanoparticles; semiconductor nanoparticles and any mixtures thereof. Preferably, the nanoparticles are functionalized over all or part of their surface by charged chemical groups. The surface chemical groups can be of varied nature and can be chosen from all the anionic or cationic groups known to those skilled in the art. As examples of charged chemical groups, mention may in particular be made of carboxylate groups, sulphate groups, phenolate groups, ammonium groups. Thus according to one embodiment, the nanoparticles are hybrid organic-inorganic compounds.

The functionalization of the surface of the nanoparticles can be carried out by any known method and in particular by the deposition of one or more coating layers or even by grafting of chemical groups.

When the nanoparticles are chosen from metallic nanoparticles, they are preferably chosen from noble metal nanoparticles such as gold (Au) nanoparticles or else platinum (Pt) nanoparticles; transition metals such as iron (Fe) nanoparticles, copper (Cu) nanoparticles and silver Ag nanoparticles; polyoxometallates and nanoparticles of any of their alloys.

When the nanoparticles are chosen from metalloid nanoparticles, they are preferably chosen from boron (B) nanoparticles, silicon (Si) nanoparticles, germanium (Ge) nanoparticles and nanoparticles of any one of their mixtures , more preferably from silicon (Si) nanoparticles and germanium (Ge) nanoparticles.

When the nanoparticles are chosen from carbon nanoparticles, they are preferably chosen from carbon nanoparticles, in particular fullerenes such as Buckminster fullerene (C60), polycyclic aromatic hydrocarbons, in particular coronene, or even from nano-graphenes and l any of their mixtures.

When the nanoparticles are chosen from semiconducting nanoparticles, they are preferably chosen from aggregates of silicon Si nanoparticles and of phosphorus P and/or arsenic As nanoparticles, aggregates of silicon Si nanoparticles and of boron B, and any mixture thereof.

The precursor chemical species or species can be introduced into the device according to the invention directly in the form of the chemical species to be extracted/accelerated or else in the form of a precursor compound, hereinafter referred to as precursor compound of the beam or even precursor compound of gaseous charged chemical species. By “precursor compound of the beam”, is meant within the meaning of the invention a chemical compound which, combined with a polymer of the invention, dissociates into precursor species capable of being accelerated to form a beam in the gas phase.

Preferably, the precursor compound of the bundle is chosen from salts, crosslinking agents of the polymer and any one of their mixtures.

According to a first variant, the precursor species or species are present in the composition directly in the form of the chemical species or species to be extracted/accelerated.

Preferably, according to this first variant, the charged chemical species or species are chosen from ions, charged nanoparticles and any of their mixtures.

The embodiments and variants detailed above in the context of ionic chemical species and in the form of nanoparticles also apply to the precursor compounds chosen according to this first variant.

According to a second variant, the precursor species of the beam are present in the composition in the form of a salt, in association with at least one counterion.

The salt can be organic or inorganic.

Preferably, the salts are chosen from inorganic salts.

More preferentially, the inorganic salts are chosen from metal salts, preferably from alkali metal and/or alkaline-earth metal halides such as, for example, cesium iodide Csl, cesium triiodide CsU, cesium fluoride CsF, alkali and/or alkaline earth metal nitrates, and any mixture thereof.

Advantageously, the inorganic salts are chosen from metal salts, preferably from alkali metal and/or alkaline-earth metal halides such as cesium iodide Csl, alkali metal and/or alkaline-earth metal nitrates, and any of their mixtures.

According to a particular embodiment, the inorganic salt is cesium triiodide CSI ₃ . Cesium triiodide is advantageous in that it has the particularity of being able to both capture (oxidant) and provide (reducer) electrons. It thus makes it possible to facilitate the management of the redox effects occurring in contact with the support element (or directly in contact with the first electrode), these redox effects advantageously making it possible to apply the ion extraction potential to the precursor composition. The reduction of this compound against the support element (or directly in contact with the first electrode) advantageously makes it possible to generate the iodide ions to be extracted.

According to a particular embodiment, the precursor species of the beam is formed in situ by decomposition of an agent crosslinking the polymer.

According to this variant, the charged chemical species to be extracted are released during the reaction between the polymer and the crosslinking agent. In particular, during the crosslinking, the crosslinking agent dissociates so as on the one hand to crosslink the polymer and on the other hand to release the precursor chemical species of the beam.

Preferably, the agent crosslinking the polymer is chosen from covalent crosslinking agents.

By “covalent crosslinking agent”, is meant within the meaning of the invention agents crosslinking the polymer by the formation of covalent bonds.

More preferably, the crosslinking agent is chosen from dihalogenated derivatives, such as dihalogenoalkanes or derivatives of polyethylene glycol functionalized by halogens or pseudohalogens (tosylates, mesylates, etc.).

Advantageously, the crosslinking agent is chosen from: polyethylene glycols functionalized with halogen or pseudo-halogen groups.

By “pseudohalogen” or “sulfonylated derivative”, is meant within the meaning of the invention mesylates, tosylates, triflates derivatives or any of their mixtures.

Advantageously, the crosslinking of the polymer is carried out at the surface of the emission zone coated with the composition. This embodiment is advantageous in that it makes it possible to immobilize the polymer on the surface of the emission zone.

The polymer

The composition also includes at least one polymer. The use of the polymer makes it possible to separate the charged chemical species before their extraction/acceleration.

Advantageously, the polymer is in electrostatic interaction and/or in dipolar interaction with the precursor species of the beam and/or a counter-ion of the precursor species of the beam.

Preferably, the polymer is chosen from polymers comprising polar groups, polymers having charged groups, crosslinkable polymers and any of their mixtures. According to a first variant, the polymer is chosen from polymers comprising polar groups. These polar groups make it possible to confer on the corresponding polymer a solvating character for the precursor species present in the composition.

By "solvating polymer" is meant in the sense of the invention a polymer in which it is possible to dissolve and stabilize charged chemical species. The ability of the polymer to solvate a charged chemical species stems directly from the presence of charged groups in the structure of the polymer. The polar groups of the polymer are in dipolar interaction with the charged chemical species, in particular in charge-dipole interaction.

This first variant is particularly suitable when the precursor species of the beam is present in the composition in the form of a salt, in association with a counterion.

Preferably, according to this first variant, the polymer is a polymer solvating the counterion of the precursor species of the beam.

Such polymers are chosen in particular from polyethylene glycol, polypropylene glycol and their derivatives.

Thus, according to this first variant, the counterion and the polar groups of the polymer are in charge-dipole interaction. The existence of this charge-dipole interaction between the counter-ion and the polar groups thus makes it possible to separate the precursor species from its counter-ion, thus facilitating its extraction/acceleration.

According to a second variant, the polymer is chosen from polymers having charged groups.

Preferably, according to this second variant, the polymer is chosen from ionomers.

This second variant is particularly suitable when the precursor species of the beam is present in the composition directly in the form of the charged chemical species to be extracted/accelerated, i.e. chosen from ions and charged nanoparticles.

Preferably, according to this second variant, the precursor species of the beam constitute the counter-ions of the charged groups of the polymer.

When the precursor species of the beam is chosen from compounds having a negative charge, the polymer is chosen from polymers having positively charged groups. Preferably, the polymer comprises at least one amino group, preferably chosen from primary amines, secondary amines, ternary amines, quaternary ammoniums and heterocyclic groups comprising at least one nitrogen atom (pyridine, imidazoles, triazoles, etc...).

Such polymers are chosen in particular from polyamines.

When the precursor species of the beam is chosen from compounds having a positive charge, the polymer is chosen from polymers having negatively charged groups.

Preferably, the polymer comprises at least one group chosen from sulphonate groups, carboxylate groups and phosphate groups.

Such polymers are chosen in particular from polystyrenes functionalized with sulfonate groups, tetrafluoroethylene copolymers functionalized with sulfonate groups such as NAFION®, etc.

According to one embodiment, the polymer is chosen from active redox polymers. Such polymers are advantageous in that they advantageously have the ability to reversibly capture electrons. They also advantageously allow good separation between the charged polymer and the precursor chemical species to be extracted.

By way of example of a redox-active polymer, mention may in particular be made of polycationic polymers of the bipyridinium type.

According to a third variant, the polymer is chosen from crosslinkable polymers, preferably chosen from crosslinkable polymers capable of forming charged groups by reaction with a crosslinking agent.

Preferably, according to this third variant, the polymer is chosen from polymers that can be crosslinked by the formation of covalent bonds.

More preferably, according to this third variant, the polymer is chosen from crosslinkable polymers whose crosslinking engages at least one heteroatom, in particular chosen from N, O and S. The heteroatom involved in the crosslinking may then be present in the chain of the crosslinkable polymer or be provided by the crosslinking agent.

Preferably, the heteroatom is N and S.

Advantageously, the heteroatom is a nitrogen atom. The crosslinkable polymer is for example chosen from polymers comprising heteroatoms. Such polymers are chosen in particular from polymers comprising pyridine groups such as poly(4-vinyl)pyridines, for example.

In this case, the crosslinking agent is typically chosen from alkylating agents.

By “alkylating agent”, is meant within the meaning of the invention a compound capable of adding one or more alkyl groups to an electronegative group, in particular the heteroatom(s) present in the polymer.

Among the alkylating agents suitable for the invention, mention may in particular be made of alkylating agents comprising at least one bond chosen from:

- C-X bonds, X being a halogen atom;

- C-triflate bonds; and

- C-tosylate bonds.

Thus, during the crosslinking reaction, the alkylating agent binds between two heteroatoms of different polymer chains in such a way that it causes the formation of bridges between the polymer chains. This reaction is associated on the one hand with the release in solution of charged species, in particular of halide, triflate and/or tosylate ions, and on the other hand with the appearance of charged groups in the structure of the crosslinked polymer at the level heteroatoms.

In particular, when the crosslinkable polymer is chosen from polymers comprising nitrogen atoms, the crosslinking reaction is a quaternization reaction causing the appearance of quaternary ammonium groups in the crosslinked polymer.

Alternatively, the crosslinkable polymer can be chosen from polymers comprising a nucleofuge or leaving group.

By “nucleofuge” or “leaving group”, is meant in the sense of the invention an ion or a chemical group having the capacity to detach from a molecule.

Such polymers are chosen in particular from polymers comprising halogen atoms such as for example poly(4-(chloromethyl)styrene.

In this case, the crosslinking agent is typically chosen from crosslinking agents comprising at least two heteroatoms, in particular chosen from N, O and S.

Mention may be made, by way of example, of diamines such as for example bis-pyradine.

Thus, during the crosslinking reaction, each of the heteroatoms of the crosslinking agent binds to a polymer chain, at the level of a carbon atom carrying one of the groups. This reaction thus causes on the one hand the detachment and the release in solution of the leaving group and on the other hand the formation of bridges between the chains of polymers. It also causes the appearance of charged groups in the structure of the crosslinked polymer at the level of the heteroatoms.

Process

According to one embodiment, the method according to the invention further comprises, before step 1), a step of bringing the emission zone, in particular the first electrode or the support, into contact with the composition comprising the polymer and the precursor species or species of the beam.

Preferably, the first electrode or the support is coated over all or part of its surface with a layer of the composition

This contacting step can be carried out according to any known method. It can for example be carried out by soaking the emission zone, in particular the first electrode or the support, in the composition, by manual and/or mechanical deposition of the composition, or by evaporation of the composition initially dissolved in a solvent volatile. In particular, the step of bringing the emission zone into contact with the composition can be carried out by means of fluidic equipment making it possible to transport the composition from the reservoir to the surface of the emission zone.

This contacting step may also consist of inserting or introducing the emission zone, in particular the first electrode or the support, into the reservoir comprising the composition, the reservoir having an orifice to allow the production of the beam.

According to one embodiment, the method according to the invention further comprises a step of heating the composition. This heating step can be carried out before and/or during and/or after the vacuum step.

Preferably, the composition is heated to a temperature ranging from 10 to 600°C, more preferably from 15 to 300°C, even more preferably from 20 to 120°C.

According to one embodiment, the method comprises, between step 1) and step 2), a step of putting the device under vacuum.

Preferably, the pressure inside the device during its operation is less than or equal to 10 ⁵ hPa, more preferably less than or equal to 10 ⁶ hPa.

More preferentially, the pressure inside the device during its operation ranges from 10 ⁶ hPa to 10 ³ hPa, even more preferentially from 10 ⁶ hPa to 10 ⁵ hPa. According to a particular embodiment, the precursor species of the bundle is chosen from the crosslinking agents of the polymer.

Preferably, according to this embodiment, the method according to the invention comprises an additional step of crosslinking the polymer.

Preferably, the crosslinking of the polymer is carried out directly after the step of bringing the emission zone into contact with the composition. This way of proceeding makes it possible to immobilize the polymer on the surface of the first electrode.

Uses

The invention finally relates to the use of a composition comprising at least one polymer and at least one precursor species of a bundle of charged chemical species in the gas phase as defined above in a device for the production of a beam of charged species in the gas phase, preferably in a device as defined above, or in a process for the production of a beam of charged species in the gas phase, preferably in a process as defined above.

The variants and preferred embodiments detailed above in the context of the method and device according to the invention also apply to the composition.

The device, the method and the composition according to the invention can be used for various applications, and in particular for all known applications of charged ion beams.

In particular, the device, the method and the composition defined above can be used for the analysis and structuring of the surface of materials; to carry out machining on a micro- or nanometric scale, in particular by engraving; for the realization of ion implantations or in the field of nanotechnology.

The use of the device, method or composition according to the invention is advantageous at least for the following reasons:

- the possibility of producing gaseous bundles of varied chemical nature,

- mild operating conditions, especially at room temperature,

- the absence of formation of droplets of precursor compositions thanks to the use of a polymer retained at the level of the emission zone, and

- the possibility of generating beams of complex chemical species, such as beams of charged nanoparticles.

tricks

FIG. 1 represents a diagram of an LMIS device according to the prior art. FIG. 2 represents a diagram of a device according to the invention.

FIG. 3 represents the emission zone of a device according to the invention according to a first embodiment.

FIG. 4 represents the emission zone of a device according to the invention according to a second embodiment

Figure 5 represents the results obtained by mass spectrometry of the gold target at the end of example 1.

Figure 6 shows the results obtained by X-ray photo-electron spectroscopy of the gold target at the end of example 1.

Figure 7 represents the results obtained by mass spectrometry of the silver target at the end of example 2.

Figure 8 represents the results obtained by energy dispersive analysis of the surface of the tungsten tip at the end of experiment 3.

Figure 9 represents the results obtained by energy dispersive analysis of the surface of the reservoir at the end of experiment 3.

Figure 10 represents the results obtained by energy dispersive analysis of the surface of the target at the end of experiment 3.

FIG. 11 represents the results obtained by X-ray photoelectron spectroscopy of the surface of the reception zone at the end of experiment 4 (curve 1), of the starting polymer NAFION®.Cs (curve 2) and of a sample of cesium carbonate CS2CO3 (curve 3).

A device according to the invention is shown in Figure 2.

The device 10 comprises an emission zone 12 and a zone 14 for receiving a beam of charged species in the gaseous phase 26. The emission zone 12 consists of a first electrode 16 and an extracting electrode 18 The first electrode 16 is coated with a precursor composition 20 comprising at least one polymer and at least one precursor compound of the beam (not shown). The precursor composition 20 is placed in a reservoir 22, having the shape of a capillary centered around the first electrode 16. The extracting electrode 18 has the shape of a ring. It is placed opposite the first electrode 16, centered with respect to the end of the first electrode 16, so as to allow the passage of the beam of charged species through the extractor electrode 18. The device 10 is also equipped with means 24 making it possible to induce a potential difference between the first electrode 16 and the extracting electrode 18 leading to the production of the beam 26. The reception zone 14 comprises a third electrode 28, placed opposite the end of the first electrode 16. The device finally comprises means 30 making it possible to induce a potential difference between the emission zone 12 and the third electrode 28 making it possible to focus the beam 26 in the direction of the reception zone 14.

The emission zone 12 comprises an element 32 making it possible to maintain a reservoir 22 having the shape of a capillary. A tip 34 crosses the reservoir 22 right through along the central axis of the reservoir 22 so that the end 36 of the tip 34 protrudes with respect to the reservoir 22. The precursor composition 20 is placed between the tip 34 and the inner surface of reservoir 22. Heating means 38 are arranged around reservoir 22. A first electrode (not shown) is connected to tip 34.

The end 36 of the tip 34 thus constitutes the end 40 of the emission zone 12 of the device according to the invention.

FIG. 4 represents the emission zone of a device according to the invention according to a second embodiment.

The emission zone 12 comprises an element 32 making it possible to maintain a reservoir 22 having the shape of a capillary. A point 34 is placed in the heart of the tank 22 along the central axis of the tank 22. Unlike FIG. 3, the point 34 does not cross the tank 22. The end 36 of the point 34 is thus located inside of the reservoir 22. The precursor composition 20 is placed between the tip 34 and the inner surface of the reservoir 22 and extends along the central axis of the reservoir so as to protrude with respect to the reservoir 22. Heating means 38 are arranged around reservoir 22. A first electrode (not shown) is connected to tip 34.

The end 40 of the emission zone 12 is thus constituted by the zone where the composition 20 protrudes with respect to the reservoir 22. The end 36 of the tip 34 is recessed with respect to the end 40 of the zone issue 12.

Examples

The following examples are given by way of illustration and in no way limit the scope of the invention. In the examples which follow, all the percentages are given by weight, unless otherwise indicated, and the temperature is expressed in degrees Celsius unless otherwise indicated, and the pressure is atmospheric pressure, unless otherwise indicated.

Example 1 - Source of iodide ions at ambient temperature and ambient pressure

The device

The device used corresponds to the device of Figure 2 except that it does not include a third electrode.

The first electrode consists of a tungsten wire W with a diameter of 0.15 mm.

The extractor electrode consists of an aluminum plate that also serves as a support for the reception area.

The reservoir consists of a glass capillary with an internal diameter of 200 µm.

The composition is a mixture of cesium iodide Csl and polyethylene glycol PEG600 (1/10 by weight of Csl, i.e. a concentration of 0.43 mol.L ⁻¹ ; i.e. 23 mol% of Csl per PEG600).

The reservoir is filled with the composition. The tungsten wire W is then introduced into the capillary up to a distance of 3 mm from the opposite end of the capillary. The beam reception zone consists of a gold plate, placed at a distance of 50 mm from the end of the capillary, on the Al aluminum plate.

A potential difference is applied between the first electrode and the extractor electrode by means of a high voltage supply.

No means of heating or vacuuming the device is used.

Results and discussion

The formation of an ion current is observed with a voltage of -6.8 kV. In particular, the formation of a yellowish-colored Taylor cone and the emission of a violet-colored beam are observed.

The implantation of iodide I ions on the gold plate is confirmed by time-of-flight mass spectrometry (TOF-MS) analyzes and by X-ray photo-electron spectroscopy. (XPS in English for “X-ray photoelectron spectroscopy”).

The mass spectrometry analyzes are carried out on the Andromeda instrument of the Institute of Nuclear Physics of Orsay (IPNO - https://andromede.in2p3.fr) which is a 1 m time-of-flight spectrometer whose voltage of The acceleration is -10 kV and the beam is a 12 MeV ^{AUIOO 4+ gold beam.} The surface analyzed is 400 μm in diameter and the impact number is approximately 2 10 ⁴ NPs/cm ² . XPS analyzes are performed with a Thermofisher Scientific K-

Alpha.

The results obtained are shown respectively in Figures 5 and 6.

Figure 5 shows the presence of peaks characteristic of the presence of iodine and gold salts. The peak at 324 m/z (peak P1) indicates the presence of gold monoiodide Aul and the peak at 451 m/z (peak P2) reflects the presence of gold diiodide Aul2.

Figure 6 shows the presence of peaks characteristic of the presence of iodine and gold salts. The peaks at 89 eV (peak P3, Au 4f ^5/2 ) and at 85 eV (peak P4, Au 4f ^7/2 ) indicate the presence of gold monoiodide Aul.

Example 2 - Source of iodide ions with heating and reduced pressure

The device

The first electrode consists of a tungsten wire W with a diameter of 0.15 mm.

The extractor electrode consists of a carbon C Faraday cage, in which is placed a plate of silver Ag constituting the reception zone of the beam.

The reservoir consists of a ceramic capillary with an internal diameter of 500 µm. The tank ends at one of its ends with a pierced cone whose final diameter is equal to 100 pm.

The composition is a mixture of cesium iodide Csl and polyethylene glycol PEG600 (1/10 by weight of Csl, ie a concentration of 0.43 mol.L ⁻¹ ; 23% in moles of CSI per PEG600).

The reservoir is filled with the composition. The tungsten wire W is then introduced into the capillary up to a distance of 2 mm from the end of the cone. A molybdenum Mo filament (diameter 0.19 mm), connected to a generator, is then wound around the reservoir so as to heat the composition.

The silver plate is placed at a distance of 20 mm from the end of the capillary.

The device further comprises a turbo-molecular pumping system, associated with a primary vane pump, making it possible to reach a pressure of 10 ⁶ hPa within the device.

Results and discussion

The production of an ion beam is obtained with the following conditions:

- Heating power: 1.3A-1.0V,

- Acceleration voltage: U(En) = -9 kV, - Extraction current: l(extraction) = from 30 mA to 60 mA, and

- Faraday current is l(F) = from -20 to -120 pA.

After 1 hour of operation, the source is switched off and the implantation of iodide ions on the silver plate is analyzed by ion imaging and by time-of-flight mass spectrometry.

Analysis by optical imaging shows the presence of I ions and Agh ions distributed homogeneously on the surface of the silver sheet.

The time-of-flight mass spectrometry analyzes are carried out using an instrument of the IONTOF IV hybrid type, marketed by the company IONTOF. The beam used is Bi ₃ ⁺ of 25 keV analyzing a surface of 250×250 pm ² . The dose is 5.4×10 ¹¹ ions/cm ² .

The mass spectrometer obtained is shown in Figure 7. The presence of peaks characteristic of the presence of iodine and silver salts is observed. The peak at 127 m/z (peak P5) reflects the presence of iodide I ions, the peak at 341 m/z (peak P6) reflects the presence of silver iodide aggregates of formula Ag2l and the peak at 361 m/z (peak P7) reflects the presence of another type of silver iodide aggregates of formula Agh.

These results confirm the implantation of iodide I ions in the silver foil. Iodine beam production is demonstrated.

Example 3 - Source of cesium ions from cesium polystyrene sulfonate

The device

The device used corresponds to the device in Figure 2.

The first electrode is in Tungsten W.

The extractor electrode, consisting of a stainless steel ring pierced in its center (diameter of the hole = 2 mm), is placed opposite the first electrode, at a millimetric distance.

The third electrode is silver Ag.

The emission zone consists of a standard LMIS-type source support comprising a cylindrical reservoir made of 100 μm W tungsten wire and the extractor electrode defined above. A 200 µm W tungsten tip is introduced into the reservoir to facilitate the formation of the Taylor cone.

The reservoir is filled with a precursor composition consisting of a cesium polystyrene sulphonate type polymer (PSS.Cs). The source is placed in a standard body of LMIS sources (called cartridge). The device also comprises a turbo-molecular pumping system, associated with a primary vane pump, making it possible to reach a pressure of 3.10 ⁶ hPa within the device.

The beam intensity is measured at the third electrode.

Results and discussions

The production of an ion beam is obtained with the following conditions:

- Heating power: 1.6V-2.0V

- Acceleration voltage: U(En) = +4 kV

- Extraction voltage: U(Extractor) = -8 kV

- Beam intensity: l(extraction) = 30 mA to 50 mA.

After 40 minutes of operation, the source is switched off and the implantation of cesium ions is analyzed. The surfaces of the tungsten tip, the reservoir and the extractor electrode are characterized by scanning electron microscopy (SEM) and by energy-dispersive analysis (EDS for “Energy-dispersive X-ray spectroscopy”).

The microscope used is marketed by the company Zeiss, under the reference MEB-FEG ZEISS Sigma HD. The beam intensity is 10 nA with an accelerator voltage of 15 kV. The magnification is 11500, which makes it possible to produce images of 100 to 10000 pm ² of surface and to measure the X-rays emitted from the surfaces studied and to deduce the elementary chemical composition therefrom.

The results obtained are represented in FIGS. 8 to 10. Peaks P8a, P9a, P10a, P8b, P9b, P10b are linked to the presence of cesium. The intensity of the peaks depends on the cesium content in the sample.

It is observed that the ionic polymer located at the level of the end of the tungsten tip has a reduced content of cesium Cs ⁺ ions, compared to the polymer present at the surface of the reservoir. The presence of cesium Cs ⁺ ions at the surface of the extractor electrode is also observed.

An analysis by X-ray photo-electron spectroscopy makes it possible to measure the molar ratio between the Cs ⁺ ions and the sulfur atoms present in the polymer. In the starting polymer, the Cs/S ratio is equal to 0.67 against a value of 0.27 at the end of the test.

This test demonstrates the ionic separation within the liquid and the extraction of cesium Cs ⁺ ions from the ionic polymer PSS.Cs. Example 4 - Cesium ion source from cesium NAFION®

The device

The device used corresponds to the device in Figure 2.

The first electrode consists of a tungsten tip (wire with a diameter of 0.15 mm).

The third electrode is a carbon Faraday cage.

The source, consisting of a stainless steel capillary with an internal diameter of 1 mm at its end, is filled with a cesium salt of a NAFION® type polymer (Cs. Nation). The source is placed in a standard body of LMIS sources called “cartridge” comprising the extraction electrode defined above. The first electrode is then introduced into the capillary to facilitate the formation of the Taylor cone. Around the cylindrical body a Mo filament (diameter 0.19) was wound to heat the source.

A turbo-molecular pumping system, associated with a primary vane pump, makes it possible to reach an operating pressure of 1.5 10 ⁶ hPa,

Results and discussions

The production of the ion beam is obtained for the following conditions:

- Heating power: from 1.0V-2.1 A to 1.5V-2.5A,

- Acceleration voltage: U(En) = +12 kV,

- Extraction voltage: U(Extractor) = -9 kV,

- Source current: l(extraction) = from 1 mA to 180 mA,

- Current of extracted ions: l(Faraday) = 3 pA at 190 nA.

After 2 hours of operation, the source is switched off and the implantation of the ions on the surface of the extraction electrode is analyzed.

The starting polymer and the surface of the extractor electrode are analyzed by X-ray photoelectron spectroscopy (XPS). The results obtained are shown in Figure 11.

Curve (1) represents the spectrum obtained by analyzing the surface of the extractor electrode.

Curve (2) represents the spectrum obtained by analysis of the starting polymer.

Curve (3), used as a comparison, represents the spectrum obtained from cesium carbonate CS2CO3. The P10 peaks are characteristic of the presence of sulfur S (2p ^3/2 and 2p ^1/2 ). Peaks P11 and P12 are characteristic of the presence of cesium (4p ^3/2 and 4p ^1/2 ).

Analysis of the surface of the extractor electrode (curve 1) shows the disappearance of the sulfur signals in comparison with what is observed for the starting polymer (curve 2). We therefore observe cesium Cs independently of sulphur. Furthermore, the spectrum obtained from the surface of the extractor electrode (curve 1) is identical to the spectrum of cesium Cs ⁺ ions recorded in the CS2CO3 salt (curve 3). These results confirm the selective extraction of Cs ⁺ ions from the NAFION® Cs ionic polymer.

Example 5 - Source of iodide ions from cesium triiodide (CsU)

Cesium triiodide Cs is prepared by reaction between 10.038g of ultra-dry cesium iodide Csl (supplier: ABCR) and diode I2 (9.83g, ALdrich) in 20mL of methanol (previously distilled over magnesium). After reacting overnight with stirring at ambient temperature, the methanol is evaporated off. The resulting black solid is then dried under vacuum. Cesium triiodide is obtained as a black microcrystalline powder, with quantitative yield.

Operation at atmospheric pressure

1.093g of cesium triiodide Cs are dissolved in 3.655g of polyethylene glycol (PEG) with a molar mass of 600, (corresponding to a concentration of 23% by mass of salt) in a 20mL single-neck flask under an argon atmosphere. When dissolution is complete, the resulting solution is introduced into a device similar to that shown in Figure 2, the reservoir having a bent shape.

A negative potential is applied at the first electrode, and is gradually increased until a current appears. The potential corresponding to the appearance of a current is -2.5 KV. A stable current of 30 microamps is observed between the source and the target surface.

An XPS analysis of the ions extracted from the source (collected on an aluminum target) shows the very predominant presence of iodine. This confirms the selective extraction of iodide I ions. The results of the XPS analysis are reported in Table 1 below.

Table 1

Ultra-high vacuum operation

A solution of 0.323 g of cesium triiodide Csl3, 1.51 g of PEG 600, and 0.077 g (5% by weight) of sorbitol (Aldrich) or glycerol (Aldrich) are introduced into a device similar to that shown in Figure 2 , the reservoir having a bent shape.

The charged source is then placed under ultrahigh vacuum (10-6 mm Hg).

The appearance of the Taylor cone is observed under the effect of an applied potential of - 2.46KV.

Example 6 - Source of fluoride ions from cesium fluoride (CsF)

A solution of 0.075 g of cesium fluoride CsF in 1.5 g of PEG 600 (corresponding to 5% by weight of CsF) is loaded into a device similar to that shown in FIG. 2, the reservoir having an angled shape.

We observe the appearance of an extraction of ions under application of a potential of - 2.5 K V. A stable source/target current of 22 microamperes is observed. The ions extracted from the source were collected on a target (aluminum foil). The XPS analysis of this deposit shows the very majority presence of fluorine on this target, confirming the selective extraction of the fluoride ions F\ The results of the XPS analysis are reported in Table 2 below.

Table 2

Example 7 - Source using redox-active polymers (poycationic polymers of the bipyridinium type)

Synthesis of the Polymer Polymer

A solution of 1.005g of 4.4' bipyridine (Aldrich) and 3.0504g of penta(ethylene glycol) ditosylate (Eburon organics) in 10mL of DMF is heated at 120°C for 24h.

After returning to ambient temperature, the polymer is precipitated in 200 mL of diethyl ether with vigorous stirring. The viscous oil thus obtained is dissolved in a dichloromethane/ethanol mixture (50/50) and the solution thus obtained is evaporated under vacuum.

The synthesized polymer corresponds to the following formula (I): Formation of a beam of tosylate ions

0.467 g of the polypyridinium are dissolved in 2.405 g of PEG 600. After heating at 100° C. for 5 hours, a limpid light brown solution is obtained. This solution is then loaded into a device similar to that shown in Figure 2, the reservoir having a bent shape.

Under the application of a negative potential of -2.5 KV, the formation of a Taylor cone is observed with emission of tosylate ions.

Example 8 - Source using cross-linked polymers.

0.614 g of penta(ethyleneglycol) ditosylate (Eburon organics), 0.060 g of poly(4-vinylpyridine) and 0.2 g of CsBr are dissolved in 3 mL of methanol at ambient temperature.

The methanol is then evaporated, and the resulting viscous liquid is then introduced into a device similar to that shown in Figure 2, the reservoir having a bent shape.

The whole is then steamed at 120°C overnight. The source thus charged is then placed under ultrahigh vacuum (10-6 mm Fig). The application of a negative potential (-9KV) leads to the appearance of a current of 100pA on a Faraday cage placed at a distance from the source. The XPS analysis of the target surface placed in the Faraday cage makes it possible to observe in particular the tosylate ions emitted by the source.

Claims

1. Process for the production of a beam of one or more charged chemical species in the gas phase, this process comprising:

1) the supply of a device comprising:

- a zone for receiving said beam,

2) the application of a potential difference between the emission zone and the reception zone,

4) beam production.

2. Method according to claim 1, in which the emission zone is heated to a temperature ranging from 15°C to 600°C, preferably from 20°C to 300°C.

3. Method according to any one of the preceding claims, in which the device comprises a reservoir making it possible to contain the composition.

4. Method according to any one of the preceding claims, in which the precursor species of the beam are in the form of a salt, in association with a counterion.

5. Process according to claim 4, in which the polymer comprises polar groups in dipolar interaction with the said counter-ion, preferably the polar groups of the polymer and the said counter-ion are in charge-dipole interaction.

6. Method according to any one of claims 1 to 3, in which the polymer comprises charged groups and in which the precursor species of the beam is a counter-ion of the said charged groups of the polymer.

7. Process according to claim 6, in which the polymer is chosen from crosslinkable polymers capable of forming charged groups by reaction with a crosslinking agent.

8. Process according to claim 7, in which the precursor species of the beam is formed during the crosslinking reaction of the polymer, preferably by decomposition of a crosslinking agent.

9. Method according to any one of the preceding claims, in which the precursor species of the beam is chosen from: monatomic ions, charged molecules, charged nanoparticles and any one of their mixtures.

10. Process according to claim 9, in which the precursor species of the beam is chosen from monatomic ions, preferably from cesium Cs ⁺ ions, iodide I ions and any one of their mixtures.

11. Process according to claim 9, in which the precursor species of the beam is chosen from pluriatomic ions, preferably nitrate ions NO ₃ , triiodide ions I ₃ , tribromide ions Br ₃ , perchlorate ions CIO ₄ , azide ions N ₃ and any one of their mixtures.

12. Method according to claim 9, in which the precursor species of the beam is chosen from nanoparticles, preferably from metallic nanoparticles, metalloid nanoparticles, carbonaceous nanoparticles, semiconductor nanoparticles and any one of their mixtures .

13. Device for implementing the method according to any one of the preceding claims, said device comprising:

- a beam reception area, and

- means making it possible to induce a potential difference between said emission zone and said reception zone.

14. Use of a composition comprising at least one polymer and at least one precursor species of a beam of charged chemical species in the gas phase in a device for the production of a beam of charged species in the gas phase, or in a method for producing a charged species beam in the gas phase.

15. Use according to claim 14, in a device for the production of a beam of charged species in the gaseous phase as defined in claim 13.

16. Use according to claim 14, in a process for the production of a charged species beam in the gas phase as defined in any one of claims 1 to 12.