This invention relates in general to devices, for generating ion beams. One non-limiting application is conventional mass spectrometry, using a beam generator as the first operational portion, in order to create an ion beam to be analysed. Other applications are however targeted, in particular in the field of secondary ion mass spectroscopy.
From a manufacturing standpoint, the invention can allow for the use of microelectronics techniques in such a way as to implement the beam generator (and possible other components) in a micro or nano electromechanical device (corresponding to the term MEMS or NEMS).
Mass spectrometers are powerful scientific instruments that allow for chemical and biological analyses in such a way as to determine compositions. Usually, these apparatuses are relatively massive and typically intended for use in the laboratory. Efforts however have been made in terms of compactness and portability without however giving full satisfaction.
Patent publication US2009/0090862 A1 presents in this context a mass spectrometer seeking to limit the footprint of this device.
An electromagnetic discrimination device is then configured to influence differently according to their mass the ions to a detector D at the end of the mass spectrometry analysis chain, on the right side of
However, such a device does not allow for an optimum extraction of ions.
It is therefore an object of the invention to overcome at least in part the disadvantages of the current techniques.
A non-limiting aspect of the invention relates to an ion beam generator, comprising:
Advantageously, it comprises at least two electrodes configured to generate a voltage gradient in the impact zone, with the voltage gradient tending to direct the ions generated to the outlet zone of the generator.
According to a preferred embodiment, the extractor comprises a first electrode referred to as input electrode laterally bordering the impact zone, and at least one second electrode referred to as intermediate electrode located in said impact zone.
As such, the extraction of the ions is produced according to a path that is as short as possible as soon as they are generated. The desired direction for the exit of the ions is applied right from the ionisation phase, contrary to prior art, wherein the ions are first directed rather randomly according to the impact of the ionising particle, then reoriented by the extractor, outside the ionisation chamber. This results in that the recovery rate of ions at the outlet of the generator is improved.
Another separable aspect of this invention relates to a mass spectrometer provided with such a generator. A method of manufacturing is also covered.
Other characteristics, purposes and advantages of this invention shall appear when reading the following detailed description, with respect to the annexed drawings, provided as non-limiting examples, and wherein:
The drawings are given by way of examples and do not limit the invention. They form block diagrams intended to facilitate the understanding of the invention and are not necessarily to the scale of the practical applications.
Before beginning a detailed review of embodiments of the invention, hereinafter are mentioned optional characteristics that can possible be used according to any association or alternatively:
Possibly, the following options are also possible:
It is specified that, in the framework of this invention, the term “on” or “above” does not necessarily mean “in contact with”. As such, for example, the deposition of a layer on another layer does not necessarily means that the two layers are directly in contact with one another but this means that one of the layers covers at least partially the other by being either directly in contact with it, or by being separated from it by a film, another layer or another element. One layer can moreover be comprised of several sublayers of the same material or of different materials.
The term intermediate position means a position strictly comprised between a first position and a second position.
In particular in what follows, the first and second positions correspondent respectively to a first end and to a second end of the extractor, more preferably in the plane XY and according to the direction X of the orthonormal coordinate system attached to the figures.
It is specified that in the framework of this invention, the thickness of a layer or of a substrate is measured according to a direction perpendicular to the surface according to which this layer or this substrate has its maximum extension. The thickness is taken in particular according to the direction Z of the orthonormal coordinate system attached to the figures.
Certain portions of the device of the invention can have an electrical function. Some are used for electrical conduction properties and the term electrode or equivalent means elements formed from at least one material that has sufficient conductivity, in the application, to carry out the desired function.
The ion generator 0 can be implemented in a more general device, in particular a mass spectrometer. This is shown highly diagrammatically in
An example of an ion generator 0 that makes it possible to obtain the result of the invention is shown as a top view (corresponding to a plane XY in the coordinate system indicated) in
Conventionally, ionisation consists in electrically charging molecules and/or atoms present in the fluid to be analysed, with the electric charge then making it possible to influence the ions generated thanks to electric fields to operate for example an acceleration and/or detection operations. The step of ionisation is diagrammatically shown in
Generally, it is preferable that the average direction of the particles charged during the bombardment be transversal, and preferably perpendicular, to an average direction of the path of the molecules and/or of atoms in the generator, in particular along the direction of extraction represented here by the axis X. Preferably, the average direction of bombardment is also perpendicular to the base 4 of the generator (typically a face of a participating substrate in the generator), while the extraction of the ions 8 is operating in the base plane 4.
The ionising particles 6 can also be photons or ions.
Thanks to this principle of ionisation via impact, ions 8 are generated. Note that these steps are advantageously produced in an enclosure wherein a depression is applied in such a way as to favour the evolution of the ions 8, and also the fluidic sample, to a direction downstream from the generator.
Characteristically, within the impact zone 9 on which the ionisation is produced, voltage gradient is furthermore applied configured to immediately influence the ions generated in such a way that it is directed to an outlet zone of the generator. In the case of
To achieve this, a plurality of electrodes 5a, b, c are used configured to generate the voltage gradient, advantageously linear. Preferably, the voltage gradient is strictly oriented along the X axis. The generator can include a programmable circuit with several control outlets each able to set the potential of an electrode.
While it could have been thought that the presence of electrodes was incompatible with the ionisation phase, as the electrodes are able to constitute obstacles to the bombardment of charged particles, this invention offers a solution in this unexpected direction, including, in a preferred embodiment, by placing electrodes all or in part in the impact zone 9.
This is the case in the example given in
The plurality of electrodes furthermore advantageously comprises at least one other electrode which can in particular be an intermediate electrode 5b.
Advantageously, the space between the electrodes 5a, 5b and 5c is constant.
In the case shown, an intermediate electrode 5b follows the input electrode 5a along the direction X and can be parallel to it. According to the configuration shown, the electrodes 5b have a passage 55, visible more precisely in
The plurality of electrodes also comprises more preferably an output electrode 5c. The passage 55 of the latter corresponds to the outlet zone of the ions 8.
This output electrode 5c more preferably constitutes a second end of the extractor according to X. Preferably, the surface of the electrode 5c is more substantial than that of the intermediate electrodes 5b.
The intermediate electrodes 5b are advantageously located between the first and second ends of the extractor. They are more preferably distributed in a portion of space between the input electrode 5a and the output electrode 5c. This portion of space is more preferably strictly comprised according to X between the input 5a and output 5c electrodes.
The distribution of the intermediate electrodes 5b can be periodical. In this case, the electrostatic potential assigned to each electrode can be granted in such a way as to accelerate or decelerate the ions along X.
The distribution of the intermediate electrodes 5b can be such that the pitch between each electrode 5b is variable according to X. In particular, this pitch can decrease regularly or increase regularly according to X. In this case, the electrostatic potential assigned to each electrode can be constant in such a way as to accelerate or decelerate the ions along X, according to the distribution chosen.
Between the electrodes, when the latter have a passage 55 with a closed contour, spaces 11 are preserved in such a way as to allow for the bombardment of the charged particles. Advantageously, at least 70% of the impact zone remains exposed to the particle beam 6. According to a possibility, the chamber has a surface between 10 and 50 mm2 and for example 23 mm2 and the surface of the grids can be between 2 and 12 mm2 and for example 5.6 mm2. With the values of 23 mm2 and 5.6 mm2 exposed hereinabove, a transparency of 75% is obtained. We shall see that in other embodiments, the electrodes have an open contour, with the opening of this contour being advantageously configured to allow for the intake of charged particles 6 in the impact zone 9.
As such,
The intermediate electrodes 5b as well as the output electrode 5c are in this example provided with a first portion 52, on the base surface 4 of the generator, and with a second portion 53 placed on an elevation relative to the first portion 52 in such a way as to arrange the passage 55. The first portion 52 can in particular be formed from a conductive later added onto the substrate carrying the base surface 4. The second portion 53 can be a beam of a conductive material or an electrically conductive coating on surface of such a beam. Still in reference to
Generally, each electrode can be connected to a circuit for setting to a predetermined potential (and different for each electrode) by the intermediary of an electrical connection 54 which can include an electrically conductive track on the surface of the base 4.
As indicated hereinabove, the dimension of the output electrode 5c of the X axis can be more substantial than the corresponding dimension for the electrodes 5b. For example, this dimension can be from 1.5 to 3 times higher. This makes it possible to have a larger surface of application of a potential in order to favour the evolution of ions 8 to the outlet zone in order to extract them from the generator.
However, in the case of electrodes with closed contours particularly, it can be interesting that the intermediate electrodes 5b be not as wide along the direction X.
In the embodiment of
A rather similar arrangement is diagrammed in
The number of electrodes is not limited; for example between two and seven electrodes can be formed.
In the case where all, or some, of the electrodes are used as counter electrodes to a source electrode (a filament for example), it is desirable that their potential be adapted (according to if the ionising particles have a positive or negative charge). If these are electrons, their potential will be greater than that of the source electrode.
The indications given hereinabove for the shape of the electrodes 5a, 5b, 5c are obviously not limiting. Furthermore, they can concern only a portion of the electrodes, even a single electrode. Likewise, it is possible to combine in the same generator several forms and designs of electrodes. For example, it is possible to form intermediate electrodes 5b with an open contour, in particular as in
Note moreover that this invention does not exclude certain electrodes from not being integrated, at least in part, in the impact zone. In particular, the extraction of ions can continue with electrodes located farther downstream of this later zone.
It is moreover advantageous that the entire beam of charged particles 6 impacts a zone of the generator wherein the constituents of the sample to be ionised are introduced. It is desirable that the impact zone 9 not be larger than the zone defined by the passages of the electrodes and it can be centred on the portion of the plane defined by these passages 55, at least along one of the dimensions X and Y.
Hereinafter is given, in reference to
In the method of manufacturing proposed here by the invention for an embodiment,
In
According to a possibility, electrical contacts are created in the form of pads 28 on the exposed portion of the implantation zone 27. The result obtained is shown in
There is as such a portion of electrode with an electrically conductive nature (at least for the fact that the semi-conductivity of the substrate 21 and advantageously of the recess of the conductivity by the additional provisions taken on the implantation zones 25, 27 and the pads 28) and of a portion of the passage, on the cavity 26 in order to extract the ions 8. It is however advantageous to have a passage 55 as large as possible. To this effect, the formation can be carried out of an additional cavity beyond the cavity 26, by an overetched zone 29 shown in
Advantageously, the base material of the substrate 31 does not conduct electricity. It can be borosilicate glass or melted silica. On one of the faces of the substrate 31, the deposition is carried out of an electrically conductive layer, preferably of metallic nature. To this effect, the method can comprise a preliminary step shown in
A portion of this layer will be used to carry out one of the portions of the electrode, as a complement of the portion formed previously on the base of the second substrate 21. In order to define the portion of the layer 33 (and of the layer 32 if present), the latter is formed, for example via a technique of photolithography and of etching in such, a way as to define patterns such as shown in
In the case of a eutectic bonding, it is preferable to use for the pads 28 an alloy which has a relatively low melting point (for example less than 300° C., which is suitable for the following alloys at the least: SiAu and AlGe). In the case of a thermocompression, metals such as aluminium or an alloy such as AlSi will preferably be used. Note that if thermocompression is used, the same conditions of application of pressure can be implemented for this portion of bonding as well as for the anodic bonding of the silicon on the glass. In the case of a eutectic bonding, it will be suitable to carry out a heating of the metal portions intended for welding, so as to reach their melting point before the putting into contact of the 2 substrates.
In reference to the dimensions in depth d1, d2 and dr described hereinabove, it will be checked that d1+d2≥dr in order to ensure the putting into contact and the electrical continuity between the 2 substrates. Moreover, the following value can be defined: ((d1+d2)−dr)/dr as compression rates. Managing this value makes it possible to best adjust the stress applied in compression during the assembly of the two substrates. It is possible for example to use a value between 0.02 and 0.07 for this rate in such a way as to find a good compromise between a suitable assembly and the absence of a risk of rupture.
A deposition, such as shown in
Number | Date | Country | Kind |
---|---|---|---|
17 51540 | Feb 2017 | FR | national |
Number | Name | Date | Kind |
---|---|---|---|
5401963 | Sittler | Mar 1995 | A |
20050199805 | Freidhoff | Sep 2005 | A1 |
20070262263 | Kruit et al. | Nov 2007 | A1 |
20090090862 | Kawana et al. | Apr 2009 | A1 |
Number | Date | Country |
---|---|---|
1 826 809 | Aug 2007 | EP |
WO 2007102224 | Sep 2007 | WO |
Entry |
---|
Yoon et al. ‘Fabrication of two types of micro ion sources for a micro timer-of-flight mass spectrometer’, Jul. 5, 2007, J Micromech. Microeng. 17, 1542-1548. |
French Preliminary Search Report dated Oct. 20, 2017 in French Application 17 51540 filed on Feb. 27, 2017 (with English Translation of Categories of Cited Documents and Written Opinion). |
Charles-Marie Tassetti, et al., “A MEMS electron impact ion source integrated in a microtime-of-flight mass spectrometer,” Sensors and Actuators B: Chemical: International Journal Devoted to Research and Development of Physical and Chemical Transducers, vol. 189, 2013, pp. 173-178. |
Todd T. King, et al., “Simulation of a Miniature, Low-Power Time-of-Flight Mass Spectrometer for In Situ Analysis of Planetary Atmospheres,” Proceedings of SPIE, vol. 6959, 2008, pp. 069590E-1 to 069590E-15. |
Richard R.A. Syms, et al., “MEMS mass spectrometers: the next wave of miniaturization,” Journal of Micromechanics and Microengineering, vol. 26, No. 2, 2016, pp. 1-28. |
Andrew Malcolm, et al., “A miniature mass spectrometer for liquid chromatography applications,” Rapid Communications in Mass Spectrometry vol. 25, 2011, pp. 3281-3288. |
Eric Wapelhorst, et al., “Complex MEMS: a fully integrated TOF micro mass spectrometer,” Sensors and Actuators A, vol. 138, 2007, pp. 22-27. |
Number | Date | Country | |
---|---|---|---|
20180254175 A1 | Sep 2018 | US |