The present disclosure relates to a microfluidic MEMS device comprising a buried chamber and to a manufacturing process thereof. In particular, in the following description reference will be made to a fluid ejection device, based on piezoelectric technology, such as an inkjet head for printing applications, a microactuator, such as a micropump, and the like.
The microfluidic device, with suitable modifications, may however also be used for the emission of fluids other than ink, e.g., for applications in the biological or biomedical field, for local application of biological material (e.g., DNA) in manufacturing sensors for biological analysis, for fabric or ceramic decoration and in 3D printing and additive manufacturing applications.
Furthermore, it may be a different microactuator, for example a micro-switch and the like.
Multiple types of fluid ejection devices processed with the MEMS (Micro-Electro-Mechanical System) technique are known.
These devices are currently formed by coupling a large number of pre-processed and assembled components in a final manufacturing step.
For example,
The nozzle portion 2 has an ejection channel 10 (also referred to as nozzle 10) and delimits downwardly a fluid containment chamber 11.
The chamber portion 3 is formed by a body 5, of silicon, and by a membrane layer 6, e.g., of silicon oxide. The fluid containment chamber 11 is delimited laterally by the body 5 and upwardly by the membrane layer 6. The zone of the membrane layer 6 above the fluid containment chamber 11 forms a membrane 7. The membrane layer 6 is of a thickness such that it may deflect.
The distribution portion 4 is of silicon and upwardly delimits an actuator chamber 12 that is downwardly closed by the membrane layer 5 and superimposed on the fluid containment chamber 11 and on the membrane 7. The distribution portion 4 has a supply channel 13, in communication with the fluid containment chamber 11 through a corresponding opening 14 in the membrane layer 6.
A piezoelectric actuator 15 is arranged above the membrane 7, in the actuator chamber 12. The piezoelectric actuator 15 comprises a pair of electrodes 21, 22, mutually superimposed, having a piezoelectric layer 20, e.g., PZT (Pb, Zr, TiO3), extending therebetween. The ejection device 1 may comprise a plurality of fluid containment chambers 11, extending side by side, laterally separated by walls 19, but mutually connected at the ends, as illustrated in
In use, a fluid or liquid to be ejected is provided to the fluid containment chamber 11 through the supply channel 13 (arrow 23); the piezoelectric actuator 15 is controlled through the electrodes 21, 22 (suitably biased) in such a way as to generate a deflection of the membrane 7 towards the inside of the fluid containment chamber 11 and a movement of the fluid towards the nozzle 10, causing a controlled ejection of a drop of fluid towards the outside of the ejection device 1 (arrow 24).
Then, the piezoelectric actuator 15 is controlled in the opposite direction, so to increase the volume of the fluid containment chamber 11 and cause further fluid to be drawn.
By cyclically repeating the actuation of the piezoelectric actuator 15, the ejection of further fluid drops is obtained.
The ejection device 1 may be manufactured as described in patent application US 2017/182778. The manufacturing process described therein provides for coupling three, at least partially pre-processed.
This coupling (e.g., by bonding techniques) generally requires high accuracy in order to obtain a good alignment between the wafers and between the functional elements formed therein.
Furthermore, the use of three wafers is expensive and, in some situations, may lead to yield problems and technological difficulties.
Patent application US 2020/0324545 describes a process for manufacturing a fluid ejection device that uses two silicon wafers and a nozzle plate formed by a dry film.
Although this solution solves the problem of using three silicon wafers, it is susceptible of improvement, as the material of the nozzle plate is not always able to ensure repeatability and uniformity of the technological process, useful in some applications, and may be incompatible with some liquids. Furthermore, the use of a polymeric material for the nozzle plate may be incompatible with applications where parts operate at low or high temperatures.
According to the present disclosure, a microfluidic device and a manufacturing process thereof are provided.
The present disclosure is directed to a device that includes a substrate having a buried cavity; a membrane layer over at least a portion of the substrate, the membrane layer includes non-permeable polycrystalline portions and permeable polycrystalline portions; an actuator coupled to the substrate, the membrane being between the buried cavity and the actuator; a cap over at least the actuator; and a plurality of through openings in fluidic communication with the buried cavity.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
For a better understanding of the present disclosure, some embodiments thereof are now described, purely by way of non-limiting example, with reference to the attached drawings, wherein:
The following description refers to the arrangement shown; consequently, expressions such as “above,” “below,” “top,” “bottom,” “right,” “left” relate to the attached figures and are not to be intended in a limiting manner.
The portions 34 of the carrying layer 33 form a closed wall, hereinafter also referred to as stop wall 34, which laterally surrounds a sacrificial portion of the sacrificial layer 32, indicated by 32A, where a cavity is to be formed, as explained in detail below.
For example, the stop wall 34 forms a hollow rectangular wall, as represented in the top view of
In particular, to form the structure of
The sacrificial layer 32 may have a thickness comprised between 0.5 and 5 μm, according to the desired depth of the structures to be formed, as described below.
The carrying layer 33 may have a thickness comprised between 1 and 20 μm, according to the expected design characteristics.
In
The release holes 36 extend throughout the thickness of the carrying layer 33 and have, for example, a circular area with a diameter d comprised between 0.5 and 2 μm. The release holes 36 are in a number and at a distance such that they allow, in a subsequent release step, the uniform flow of the etchant and maintain sufficient mechanical solidity of the carrying layer 33. For example, in order to obtain a membrane with a length equal to 25 μm, four release holes 36, arranged along a line, may be formed.
In general, the release holes 36 may be distributed throughout the area of the sacrificial portion 32A, where it is desired to create the cavity, based on technological considerations.
In
In particular, the permeable layer 37 coats the walls and the bottom of the release holes 36.
Then, the sacrificial portion 32A is etched using an etchant, for example vapor-phase HF. Due to the permeability of the permeable layer 37, the etchant traverses it and removes the sacrificial portion 32A, arranged below the release holes 36. In this manner, a buried cavity 38 is formed.
The stop wall 34 here laterally stops etching of the sacrificial layer 32, limiting it to the sacrificial portion 32A, and thus forming a wall that delimits the buried cavity 38.
Subsequently,
To this end, for example, a polycrystalline silicon layer is deposited, with a thickness comprised between 2 and 25 μm, which may be subsequently planarized and thinned, to obtain a desired final thickness, for example a thickness varying between 1 and 24 μm.
During sealing of the release holes 36, the permeable layer 37 forms a barrier against polycrystalline silicon deposition inside the buried cavity 38.
In this step, the permeable layer 37 generally changes crystallographic state and, at the end of the sealing process, it presents a structure that is no longer permeable, but polycrystalline.
Furthermore, at the end of the sealing process, the permeable layer 37 (hereinafter referred to as the non-permeable polycrystalline layer 37′) has grains with smaller size than the carrying layer 33 and the sealing layer 39.
In particular, on average, it may have grains smaller by an order of magnitude than the carrying layer 33 and the sealing layer 39. For example, the grains of the non-permeable polycrystalline layer 37′ may have dimensions of 100-500 nm while the grains of the carrying 33 and sealing 39 layers may be 500-5000 nm.
Furthermore, as shown in the detail of
In
The carrying layer 33, the non-permeable polycrystalline layer 37′, the sealing layer 39 and the insulating layer 40 form a membrane layer 41 which, on the buried cavity 38, forms a membrane 42.
In
In particular, a bottom electrode layer (e.g., formed by a TiO2 layer with a thickness comprised between 5 and 50 nm and a Pt layer with a thickness comprised between 30 and 300 nm deposited thereon) is deposited on the insulating layer 40. Then, a piezoelectric layer (for example a PZT —Pb, Zr, TiO3— layer) is deposited, having a thickness comprised between 0.5 and 3.0 μm, typically 1 or 2 μm. Subsequently, a top electrode layer, e.g., Pt or Ir or IrO2 or TiW or Ru, is deposited above the piezoelectric layer, with a thickness comprised between 30 and 300 nm. The top electrode, piezoelectric and bottom electrode layers are then patterned, to form a stack 46, comprising a bottom electrode and a top electrode, in a known and not shown manner.
In particular, the stack 46 covers almost the entire membrane 42, except for a peripheral frame.
One or more insulation and protection layers, for example, a USG, SiO2 or SiN or Al2O3 layer, single or superimposed, is then deposited with a thickness comprised between 10 nm and 1000 nm, forming a protection layer 47.
The protection layer 47 is selectively removed, to form contact openings; then a metal layer is deposited and patterned, to form contact regions 48, in direct electrical contact with the top and bottom electrodes of the stack 46, in a per se known manner. The metal layer also forms conductive tracks and pads 50, shown only schematically, for the electrical connection of the actuator element 45.
In
To this end, the membrane layer 41 is etched in a selective manner, by masked etching initially of the oxide of the insulating layer 40 and then, by a dry etching, of the silicon of sealing layer 39, non-permeable polycrystalline layer 37′ and carrying layer 33, until reaching the buried cavity 38. For example, the fluid opening 51 is formed at a first end of the buried cavity 38, making it accessible from the outside.
Furthermore, bonding and sealing regions 53 are formed on the top surface of the wafer 30, on the insulating layer 40 and/or the sealing layer 39.
The bonding and sealing regions 53 may be of polymeric material, such as BCB (Benzocyclobutene) or other suitable material and may be formed by deposition and definition or by molding.
Then,
A composite wafer 60 is thus formed.
The cap wafer 55 has been pre-processed so as to already have a recess 56 having a larger area than the actuator element 45 and delimited by a protruding edge 57 intended to couple to the bonding and sealing regions 53.
Furthermore, the cap wafer 55 already has a through opening 58, outside the recess 56.
The recess 56 and the through opening 58 are arranged so that, when the cap wafer 55 is bonded to the first wafer 30, the recess 56 is arranged over the actuator element 45, forming an actuator chamber, again indicated by 56, and the through opening 58 is arranged in continuation with the fluid opening 51, forming a first fluidic channel 59, typically a supply channel.
The cap wafer 55 may also have openings 61 for accessing the pads 50. Furthermore, the first wafer 30 is etched from the back, for example by dry etching the material of the substrate 31.
A second fluidic channel 62 is thus formed, here an outlet nozzle, which completely passes the substrate 31 and reaches the buried cavity 38, for example at a second end thereof, opposite with respect to the fluid opening 51.
As a result, the buried cavity 38 is now connected with the outside both through the first fluidic channel 59 and through the second fluidic channel 62 and forms a fluidic chamber, indicated again by 38.
Since the fluidic chamber 38 is obtained by partial removal of the sacrificial layer 32, the desired depth for the fluidic chamber 38 determines the thickness of the sacrificial layer 32.
The composite wafer 60 may then be diced to form a microfluidic device 65, as shown in
After dicing, the microfluidic device 65 of
The monolithic body 80 has a peripheral surface defining a first face 80A (top face, in the drawings) and a second face 80B (bottom face, in the drawings).
A cap element 81 extends above the monolithic body 80 and is attached to the first face 80A.
The membrane 42 comprises a bottom layer including a plurality of first polycrystalline zones 90 and a plurality of second polycrystalline zones 91.
The first polycrystalline zones 90 are formed by the non-permeable polycrystalline layer 37′ and by the filling portions of the sealing layer 39 and include a portion facing the fluidic chamber 38 having a finer crystalline structure (at the non-permeable polycrystalline layer 37′) and an overlying portion, having a coarser crystalline structure.
The second polycrystalline zones 91 (typically connected) are formed by the carrying layer 33 and have a coarser crystalline structure. In this manner, the microfluidic device 65 is formed from two wafers (first wafer 30 and cap wafer 55) only, and therefore has a simplified structure, that may be formed with simpler steps and at reduced costs.
In use, and in a manner known to the person skilled in the art, a fluid may enter the first fluidic channel 59, traverse the fluidic chamber 38 and exit the second fluidic channel 62 (or vice versa), due to the deformation of the membrane 42, caused by the actuation of the actuator element 45.
In particular, by arranging one of the bonding and sealing regions 53 so that it surrounds the recess 56, after the mutual bonding of the first wafer 30 and the cap wafer 55, the actuator chamber 56 is tight-closed and the actuator element 45 is safely insulated from the external environment.
Furthermore, by arranging one of the bonding and sealing regions 53 so that it surrounds the fluid opening 51, after the mutual bonding of the first wafer 30 and the cap wafer 55, the first fluidic channel 59 is tight-closed with respect to the rest of the device, in particular to the actuator chamber 56.
The substrate 131 may be for example of monocrystalline silicon; the sacrificial layer 132 may be of silicon oxide, obtained by thermal oxidation and have a thickness comprised between 0.5 and 5 μm (based on the desired depth of the fluidic chamber to be formed); and the carrying layer 133 may have been epitaxially grown and may have a thickness comprised between 1 and 20 μm, based on the elasticity and resistance characteristics desired for the membrane.
In
In particular, here, a membrane release hole 136A, a plurality of inlet release holes 136B and a plurality of channel release holes 136C are formed. The etching may be a dry etching.
In the illustrated example, as visible in the top view of
The inlet release holes 136B are arranged along a closed line, outside the membrane release hole 136A. The inlet release holes 136B may have any shape, e.g., circular, squared, rectangular (or other shape), with a diameter or side comprised between 0.5 and 2 μm and may be arranged at a mutual distance of a few μm (typically, from 0.1 to 0.2 μm) similarly to what has been described for the release holes 36 of
The channel release holes 136C are arranged along radial directions that connect the membrane release hole 136A to the circumference of the inlet release holes 136B. In this embodiment, the channel release holes 136C are arranged along four radial lines, placed at 45° from each other, but other arrangements are possible. The channel release holes 136C may also have a circular or squared shape (or other shape), with a diameter or side comprised between 0.5 and 2 μm and may be arranged at a mutual distance, for example comprised between 0.2 and 0.4 μm.
In
As discussed above, the permeable layer 137 has a structure characterized by micro-holes and is therefore permeable to liquids and vapors.
The permeable layer 137 here coats the walls and the bottom of the membrane release holes 136A, the inlet release holes 136B and the channel release holes 136C.
In
Due to the permeability of the permeable layer 137, the etchant traverses it and removes the portions of the sacrificial layer 132 arranged below the release holes 136A-136C and, partially, laterally thereto (in a manner not shown in
A buried cavity 138 is formed in this manner under the membrane release hole 136A.
An inlet trench 170 is formed under the inlet release holes 136B; in fact these are sufficiently close to each other to cause removal of the material of the sacrificial layer 132 along a continuous line (here, a circumference) having inlet release holes 136B extending therealong.
Furthermore, connection channels 171 (in
This is represented in
Subsequently,
To this end, for example, a polycrystalline silicon layer is deposited, with a thickness comprised between 2 and 25 μm, which may subsequently be planarized and thinned. In the embodiment shown, the silicon of the sealing layer 139 outside the release holes 136A-136C is completely removed.
In general, the removal of the sealing layer 139 outside the release holes 136A-136C may not be complete, similarly to what occurs for the sealing layer 39 of
In
The insulating layer 140 may be, also here, a TEOS (tetraethylorthosilicate) layer with a thickness of about 0.5 μm.
The carrying layer 133, the non-permeable polycrystalline layer 137′, the sealing layer 139 and the insulating layer 140 thus form a membrane layer 141 which, on the buried cavity 138, forms a membrane 142.
The actuator element 145 may be formed in the manner described above with reference to
Here, as visible from
In
A metal layer is then deposited and patterned to form contact regions (indicated, in
In
To this end, the membrane layer 141 is etched in a selective manner, first by etching the protection layer 147 and the insulating layer 140 and then, by dry etching the silicon of the sealing layer 139 and of the non-permeable polycrystalline layer 137′, at the inlet release holes 136B (
The connection channels 171 are thus formed and put the buried cavity 138 in communication with the outside through the trench 170 (
In
Then, a cap wafer 155, previously processed, is bonded to the top face of the first wafer 130, through the bonding and sealing regions 153, thus forming a composite wafer160.
In particular, the cap wafer 155 has a recess 156 with a greater area than the actuator element 145; the recess 156 is delimited by a protruding edge 157 which couples to the bonding and sealing regions 153.
Furthermore, the cap wafer 155 already has a plurality of through openings 158, arranged externally to the recess 156 and crossing the protruding edge 157.
The recess 156 and the fluid openings 151 are arranged so that, when the cap wafer 155 is bonded to the first wafer 130, the recess 156 is arranged over the actuator element 145, forming an actuator chamber, indicated again by 156, and the through openings 158 are arranged in continuation with the fluid openings 151. The through openings 158 and the fluid openings 151 together form first fluidic channels 159, typically supply channels, directly connected to the fluidic chamber 138 through the inlet trench 170 and the connection channels 171.
The cap wafer 155 may also have openings for accessing the pads 150, in a manner not shown.
In this manner, the actuator chamber 156 is sealed with respect to the outside and to the fluidic path defined by the fluid chamber 138, the connection channels 171 and the first fluidic channels 159 and tightly encloses the actuator element 145.
In
A second fluidic channel 162, typically an outlet opening, is thus formed, completely crosses the substrate 131 and reaches the fluidic chamber 138, e.g., in the center.
As a result, the fluidic chamber 138 is now connected with the outside both through the first fluidic path 171-170-159 and through the second fluidic channel 162.
The composite wafer 160 may then be diced to form a microfluidic device 165.
After dicing, the microfluidic device 165 of
The monolithic body 180 is formed here by the substrate 131, the sacrificial layer 132, the carrying layer 133 and the insulating layer 140.
A cap element 181 extends above the monolithic body 180 and is attached to the first face 180A of the monolithic body 180.
In this case, the membrane 142 is formed by a first polycrystalline zone 190 and by a second polycrystalline zone 191.
The first polycrystalline zone 190 comprises the non-permeable polycrystalline layer 137′, having a finer crystalline structure, and the filling portions of the sealing layer 139, having coarser crystalline structure.
The second polycrystalline zone 191 is formed by the carrying layer 133, surrounding the first polycrystalline zone 190 and having a coarser crystalline structure, similar to the sealing layer 139.
In use, and in a manner known to the person skilled in the art, by actuating the actuator element 145, the membrane 142 may be deflected so as to draw a fluid through the first fluidic channels 159 and the connection channels 170 towards the fluidic chamber 138; the liquid may then be pumped outwards through the second fluidic channel 162 (or vice versa).
In particular, during use, the actuator chamber 156 is tight-closed and the bonding and sealing regions 153 safely insulate the actuator element 145 from the external environment.
According to a different embodiment, an insulating layer may be deposited on the permeable layer before the formation of the sealing layer.
For example,
In detail, here, after forming the buried cavity 38, an insulating layer 44, for example of oxide, is deposited above the permeable layer 37.
Then,
In this case, the permeable layer 37 tends to maintain the previous permeability and crystallographic state characteristics.
Owing to the use of only two wafers, the described microfluidic device may be manufactured at low costs and in a simpler manner, reducing alignment operations between the wafers, and therefore with high yield.
Furthermore, processing only two wafers allows the use of a lower number of masks compared to a three-wafer process.
Finally, it is clear that modifications and variations may be made to the microfluidic device and to the manufacturing process described and illustrated herein without thereby departing from the scope of the present disclosure, as defined in the claims.
For example, the inlet and outlet channels might extend from a same face of the body accommodating the fluidic chamber 38, 138.
In addition, the microfluidic device may have a single inlet/outlet channel and operate as a buffer in a fluidic circuit.
The microfluidic device may comprise a plurality of fluidic chambers, in particular in case of manufacturing an inkjet head, arranged side by side and in connection with the ends, as shown in
For example, the different embodiments described may be combined to provide further solutions. For example, the variant of
A microfluidic device (65; 165) may be summarized as including a monolithic body (80; 180) having a peripheral surface defining a first face (80A; 180A); a fluidic chamber (38; 138) in the monolithic body; a first fluid opening (51; 151, 170) extending from the peripheral surface of the monolithic body and in fluidic communication with the fluidic chamber; a cap element (81; 181) extending above the monolithic body and attached to the first face; an actuator chamber (56; 156) extending between the cap element and the first face of the monolithic body; a membrane region (42; 142) in the monolithic body, the membrane region extending between the first face and the fluidic chamber; a piezoelectric actuator element (45; 145) extending on the first face, above the membrane region, inside the actuator chamber, wherein the membrane region (42; 142) includes at least one first zone (90; 190) and one second zone (91; 191), the at least one first zone (90; 190) including a first portion (37; 137′), facing the fluidic chamber, of polycrystalline silicon having a first crystallographic structure and a second portion (39; 139), of polycrystalline silicon, overlying the first portion and having a second crystallographic structure, and the second zone (91; 191) including a third portion (33; 133), facing the fluidic chamber (38; 138), of polycrystalline silicon having a third crystallographic structure, the first crystallographic structure having a smaller average granularity than the second and the third crystallographic structures.
The at least one first zone (90, 190) may be surrounded by the second zone (91; 191).
The at least one first zone (90) may include a plurality of first zones and the second zone (91) may include a plurality of holes (36), each surrounding a respective first zone (90).
The membrane region (42; 142) may include a stack including a carrying layer (33; 133) of silicon, a permeable layer (37; 137) of silicon, a sealing layer (39; 139) of silicon and an insulating layer (44) of insulating material, wherein, at the first zone (90, 190), the permeable layer (37; 137) may form the first portion, the insulating layer (44; 144) may overly the permeable layer (37; 137) and the sealing layer (39; 139) may form the second portion and may overly the insulating layer (44; 144), and, at the second zone, the carrying layer (33; 133) may form the third portion, the permeable layer (37; 137) may overly the carrying layer (33; 133) and the insulating layer (44) may overly the permeable layer (37; 137).
The second zone (91), the sealing layer (39) may overly the insulating layer (44).
The at least one first zone (90, 190) may form a step (43) protruding towards the inside of the fluidic chamber (38; 138) with respect to the second zone (91; 191).
The first fluid opening (51; 151) may extend between the fluidic chamber (38; 138) and the first face (80A, 180A) of the monolithic body (80; 180), the microfluidic device (65; 165) may further include a second fluid opening (62; 162) extending through the monolithic body (80; 180) between a second face (80B; 180B) of the monolithic body (80; 180) and the fluidic chamber (38; 138).
The microfluidic device may form a fluid ejection device, a micropump, a microswitch, a fluidic buffer device.
A process for manufacturing a microfluidic device may be summarized as including forming a sacrificial layer (32; 132) on a semiconductor substrate (31; 131); forming a carrying layer (33; 133) on the sacrificial layer, the carrying layer being of non-permeable semiconductor material; selectively removing the carrying layer to form at least one release opening (36; 136A) extending through the carrying layer; forming a permeable layer (37; 137) of a permeable semiconductor material in the at least one release opening; selectively removing the sacrificial layer (32; 132) through the permeable layer (37; 137) in the at least one release opening and forming a fluidic chamber (38; 138); filling the at least one release opening with non-permeable semiconductor filling material, thereby forming a monolithic body (80; 180) having a peripheral surface defining a first face (80A; 180A) and including a membrane region (42; 142) extending between the first face and the fluidic chamber; forming a piezoelectric actuator element on the first face of the monolithic body, on the membrane region, forming a first fluidic opening (51; 151) extending into the carrying layer (33, 133) until the fluidic chamber; and attaching a cap element to the first face of the monolithic body, the cap element having a recess defining, together with the monolithic body, an actuator chamber surrounding the piezoelectric actuator element.
The membrane region (42; 142) may include at least one first zone (90; 190) and one second zone (91; 191), the at least one first zone (90; 190) may include a first portion (37; 137′), of polycrystalline silicon, facing the fluidic chamber and having a first crystallographic structure, and a second portion (39; 139), of polycrystalline silicon, overlying the first portion and having a second crystallographic structure, and the second zone (91; 191) may include a third portion (33; 133), of polycrystalline silicon, facing the fluidic chamber (38; 138) and having a third crystallographic structure, the first crystallographic structure having a smaller average granularity than the second and the third crystallographic structures.
Forming a permeable layer (37; 137) may include depositing a polycrystalline silicon layer by LPCVD.
The permeable layer (37; 137) may have a thickness between 0.06 and 0.2 μm.
Filling the at least one release opening may include epitaxially growing a sealing layer (39; 139).
The sealing layer (39; 139) may have a thickness between 2 and 25 μm.
The process may further include, after selectively removing the sacrificial layer (32; 132) and before filling the at least one release opening (34; 134), depositing an insulating layer (44) such as silicon oxide.
The various embodiments described above can be combined to provide further embodiments. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents, applications and publications to provide yet further embodiments.
These and other changes can be made to the embodiments in light of the above-detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure.
Number | Date | Country | Kind |
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102021000024944 | Sep 2021 | IT | national |