Patent Grant
11841306
The present invention relates to a sensor for measuring the mass concentration of fine particles for air pollution, potentially indoor air and contamination with a biological origin.
Particulate pollution is implicated in the occurrence of various cardiovascular, cerebrovascular and respiratory pathologies through mechanisms of toxicity described by the “Haut Conseil de la Santé Publique” (HCSP) (“Pollution par les particules 2 dans l'air ambiant—Recommandations pour protéger la santé”, 2012). Atmospheric pollution and particles in the air have been classified as “definitely carcinogenic to humans” in 2013 by the International Agency for Research on Cancer (IARC) (“Monographs on the evaluation of carcinogenic risks to humans”; volume 109). This pollution has also been identified as being responsible for premature deaths, of the order of 42,000 per year in France, which compliance with the thresholds recommended by the WHO (10 and 25 μg/m3 respectively annual average and 24-hour average for PM2.5 and 20 and 50 μg/m3 respectively annual average and 24-hour average for PM10) would make it possible to reduce significantly, as highlighted in the Aphekom report (InVS and other European partners, 2011).
Currently, the reference method for the measurement of PM10 and PM2.5 mass concentrations is the gravimetric method described in the European standard “EN 12341:2014 2016”. This method of filter sampling followed by weighing under standard conditions is very cumbersome to implement and identified as “difficult to apply in the context of routine data production of measurement networks” by AIRPARIF in a summary report dated 2008 (AIRPARIF, 2008). The European standard allows the use of methods other than the gravimetric method provided that it can be proved that the measurement has a constant relationship with the reference measurements. This is generally referred to as certification via a “demonstration of equivalence to the reference method”.
There are currently three methods of continuous PM10 and PM2.5 measurements used by monitoring networks in Europe: the Beta gauge, the TEOM (Tapered Element Oscillating Microbalance) and the TEOM-FDMS (Filter Dynamics Measurement System).
It can also be noted that there are optical methods of mass concentration measurement (nephelometry) which consist of measuring the intensity of light scattered by particles passing through a measuring cell illuminated by a light source. A calibration is used to determine the mass concentration. This method, which has the advantage of being miniaturizable and inexpensive, does not make it possible to define a stable correction factor with reference measurements, which makes it unsuitable according to the standards defined by the European standard.
In the literature, other systems are available for allowing a direct real-time measurement of the mass collected on the different stages of a cascade impactor. These systems called QCM (in English “Quartz Crystal Microbalance” or in French “Microbalance a quartz”) allow to obtain the mass concentration of particles by size class corresponding to each stage of the impactor. These systems generally do not allow to obtain the total mass concentration but can however measure the mass concentration fractions such as PM10-2.5, PM2.5-1 or PM1-0.05 which can be interesting from an epidemiological point of view. It should be noted, however, that these devices are currently used very little as they have many metrological limitations (Berthelot, 2015).
From the previous elements it becomes very clear that there are currently no devices for real-time or low time step measurements, particulate mass concentrations meeting European requirements and of dimensions and operation suitable for multiple deployment in indoor or outdoor environments.
In this context, the invention concerns the development of a miniature system for the continuous monitoring of the particulate mass concentration for different particle size fractions (PM10-2.5, PM2.5-1 or PM1) of indoor or outdoor air.
The invention concerns a miniature system for the particle size analysis of particles, preferably polluting particles, suspended in the air. It comprises a miniature selection device using the aerodynamic properties of the particles as well as MEMS microbalances for mass measurement.
The present invention concerns a sensor for the in-situ and continuous analysis of an aerosol flow allowing the measurement of the mass of micronic/submicronic particles suspended in the air flow, comprising:
The invention makes it possible to develop high-performance sensors for the analysis of air quality due to particulate pollution in order to propose “alternatives” to current gravimetric systems whose sensitivity and portability are limited.
Indeed, the usual gravimetric sensors use the measurement of the resonance frequency of a mechanical oscillator. The resonance frequency is connected to its mass by
where fr is the resonant frequency, k the stiffness constant and m the mass of the oscillator. An addition of mass on the oscillator will thus cause a variation of its resonance frequency.
The minimum mass detectable by a resonator is given by:
where Q is the quality factor. So a resonant element with a low mass and a high quality factor will have a higher detection sensitivity. By using silicon micro or nano-systems, the mass of the resonator can be considerably reduced.
The invention enables the development of MEMS devices for measuring “intermediate” masses of particles, i.e. between the attogram and the nanogram. In particular, the microbalance is designed to measure an oscillation frequency shift.
The reduced size and cost of the device allows its large-scale deployment and its adaptation to the monitoring of specific environments and/or the needs of the public. Due to these characteristics, the device can also be used as individual and/or nomadic equipment. This system can also be used to evaluate new practices and offers that will accompany the policies to improve the energy and environmental performance of buildings that are being put in place.
The device can be integrated into a network/connected object/instrument and/or a building air quality management device such as a ventilation system control device.
Depending on other optional sensor features:
One of the originalities of this device resides in the co-integration of the sorting system, microbalances manufactured using silicon microfabrication technologies and automated cleaning, reference or calibration functions. The functionalization of the surface of the microbalances by adequate treatment or microstructuring allows a preferential adhesion to measure the mass concentrations of contaminants to be monitored. This device is integrated on an electronic board in order to make the processing and control of the measurement signals compact. The integration of these functions allows the use of the instrument for continuous and real time monitoring of air quality.
Other objectives, features and benefits will emerge from the detailed description that follows with reference to the drawings given for illustrative and non-limitative purposes, among which:
The present invention presents a sensor 1 for the continuous in-situ analysis of an aerosol flow, allowing the measurement of the mass of micron/submicron particles 2 suspended in the air flow and represented in
This sensor 1 includes a device of aeraulic sorting allowing to perform the granulometry of the particles 2 according to their size while integrating the measurement systems.
The device of aeraulic sorting according to the present invention:
Sensor 1 also has:
The system for cleaning allows the sensor to operate in continuous/real time, the MEMS 7 microbalances being cleaned before any new measurement of sensor 1.
As an example only and in a non-limitative way, it can be chosen time steps of every hour, every quarter of an hour, every minute, every 10 seconds, to carry out the cleaning, thus allowing periodic measurements, real time or near real time measurements. This will typically depend on: the concentrations encountered; the use made of the system.
If the regeneration of a sensor is an identified problem is known, the difficulty is to integrate and operate it in situ without “maintenance” intervention on the sensor and without damaging it. It is described in the state of the art the use of a supercritical fluid which is inapplicable without maintenance on the sensor and therefore for the present integrated system of the invention.
The solution we propose is easy to implement and can be combined with a mechanical action (by vibrating the membrane vertically or horizontally at a frequency higher than the particle detachment frequency) or with a thermal action (by integrating resistive elements under the membrane).
The schematic diagram of the system is shown in
The sampling head (filter with opening, vortex or other state of the art system) allows only PM10 particles to pass through, i.e. particles whose size, in particular the diameter, is less than 10 micrometers (PM10). A description and measurement of PM10 particles is in particular detailed in standard NF EN 12341.
The diameter of the axial nozzles at each sampling stage can be of the order of a few hundred micrometers with flow rates from 1 to several L/min. Thus, this flow rate corresponds roughly to the human ventilatory flow rate, which is between 5 and 10 L/min, whereas flow rates<0.3 L/min such as those of the system described by Maldona-Garcia et al, 2017—IEEE SENSORS JOURNAL, Vol. 17, No. 6, Mar. 15, 2017 are not very representative. Moreover, this corresponds to cut-off diameters between 100 nm and a few μm (e.g. 10 μm) in order to measure particles with an average diameter smaller than 10 micrometers. For example to measure particles from a few 100 nm to 10 μm, preferably PM10 particles with a diameter of at least 100 nm, more preferably at least 200 nm.
The aim is to provide a device compatible with the WHO standards concerning the categories of particles (PM) to be measured and their threshold values. In particular, this device allows the measurement of the thoracic fraction of particles.
Using the cascade impactor, particles 2 of different diameters are impacted at different stages 4a, 4b, 4c of the system and measured using MEMS 7 microbalance located at the impaction zones.
Indeed, depending on the opening diameter of an impactor, the air flow loaded with particles will be more or less accelerated, the particles 2 of lower inertia will follow the air flow while those of higher inertia will be impacted on a zone located under an aerosol flow nozzle located opposite the MEMS 7 microbalance.
Each stage 4a, 4b, 4c presents on the same plan:
Advantageously, the lateral openings 9 are arranged symmetrically to the axial recess 8 located centrally in the impactor body 3.
Axial nozzles 10 and axial recesses 8 are of decreasing size along the axis of the aerosol flow so as to impact particles 2 of decreasing size at each stage.
Here, it can be chosen for example a diameter and a number of lateral openings 9 located in the flow passage to allow impact:
The impactor body 3 can have a modular stack consisting of wafers 11 of silicon or other micro/nano-structured materials, for example by means of micro or nano manufacturing in clean rooms, supported and attached to each other.
For example, other possible materials are: glass, aluminum.
If flow pipe 6 is made of silicon or other micro/nano structured material, it can be covered with a conductive metal.
Here in
Here on
The inlet lateral channels 12a and outlet lateral channels 12b fluidically communicate with the flow pipe 6 to circulate a cleaning fluid, such as air or solvent or solvent+air, over the MEMS microbalances from the inlet lateral channels 12a to the outlet lateral channels 12b.
They lead to the flat surface of stage 4a, 4b, 4c, which has the axial openings 9 and the MEMS microbalances 7.
The input lateral channels 12a and output lateral channels 12b of each stage 4a, 4b, 4c are located between a silicon wafer called “spacer” 11b, 11d and the first silicon wafer 11a.
As an alternative, not shown in
In a second variant, the system for cleaning MEMS microbalance includes the oscillating membrane 7a.
In a third variant, the system for cleaning has a combination of at least two of the following three devices:
The means for controlling and flowing the aerosol flow are, for example, one or more pumps.
In a variant not shown in the diagrams, the impactor body 3 of the sensor 1 has means for opening/closing:
The silicon membranes 7a, with an electrostatically actuation (
The actuation of membrane can also be: piezoelectric or magnetic.
Each membrane 7a is suspended from several anchors 13, preferably made of silicon, to which the membrane is fixed in tension, the membrane 7a being arranged between several electrodes 14 suitable for electrostatic actuation or measurement. Advantageously, the membrane is surrounded on its circumference by the electrodes.
Here in
In the case where the actuation is electrostatic, an alternating voltage combined with a direct voltage is applied to one or more actuation electrodes 14 while the suspended membrane 7a is maintained at a zero electrostatic potential. An electrostatic force oscillating at the same frequency as the actuation voltage is thus induced on the membrane 7a.
The membrane 7a is then deformed in a planar oscillating movement. As membrane 7a is electrostatically charged, the movement of the membrane 7a induces a charging movement and thus a current proportional to the speed of movement of membrane 7a.
This current can be measured via contacts connected to the anchors 13 of membrane 7a or to an electrode not used for actuation. There are particular actuation frequencies for which the deformation amplitude of membrane 7a is maximum.
For a resonance frequency, the current measured at this frequency is maximum. With an addition of mass, this mechanical resonance frequency will vary.
The measurement of the resonance frequency therefore provides information about the deposited mass.
Advantageously, the surface of the MEMS 7a membranes of the MEMS 7 microbalances can be used to control the adhesion and/or separation (alternatively wetting/un-wetting of the cleaning fluid) of particles 2:
Eventually it can have electrostatic/mechanical or thermal properties to control the adhesion and/or separation of particles 2, when charged. For example a possibility if some aerosols are negatively charged and others rather positively charged, using electrostatic properties can also improve the deposition efficiency.
One or more layers of material can be placed on the surface of the 7a membranes of MEMS microbalances to allow preferential adhesion of target 2 particles.
Depending on the application, the surface of the 7a membranes is configured differently.
For example, the surface of the membranes 7a can be optimized to preferentially detect the mass of biological aerosols, pollens, fungi, bacteria thanks to their specific surface properties.
The surface of the membranes 7a of MEMS microbalances can be micro or nanostructured silicon, such as black silicon (shown in
Advantageously, the surface of the membranes can be coated with a polymer. In one particular realization mode, the surface of the membrane 7a is black silicon coated with a thin layer of polymer to, for example, influence the adhesion of target particles 2 to the membrane 7a or the behavior of target particles 2 with respect to the 7a membrane.
The oscillating membrane 7a was realized as shown in
The width of the oscillating membrane 7a range from several hundred microns to several millimeters. That means, at least 100 μm, or even 200 μm, 300 μm, 400 μm, preferably at least 500 μm. In addition, the oscillating membrane 7a can have a width of up to 10 millimeters, preferably up to 5 millimeters. Thickness dimensions can be between 30 μm and 50 μm or between 35 μm and 45 μm, for example.
For each MEMS 7 microbalance, the distance between the oscillating membrane 7a and the electrostatic actuators which are the electrodes is less than or equal to 1 micrometer.
The oscillating membrane 7a is preferably a rectangular or square membrane.
The oscillating membrane 7a is advantageously a rectangular membrane.
It can also have a circular shape or any other shape.
The oscillating membranes 7a of the MEMS 7 microbalances are conformed to present:
The frequencies of the membranes 7a of the MEMS microbalances are advantageously between 1 and 20 MHz.
Advantageously, the MEMS 7 microbalance is configured to allow the mass measurement of particles 2 between the attogram and the nanogram.
The resolution or accuracy of the MEMS 7 microbalance in mass measurement is the nanogram, due to the choices made to take silicon, with a specific deformation mode of the membrane 7a, and a particular shape of the 13 anchors, which allow to maximize the quality factor of the resonator while keeping a large active surface.
By the geometry of the microbalance (in particular square), its type of actuation (electrostatic) and its deformation mode (according to a volume mode in the plane) in Lamé or extensional mode, which makes it possible to guarantee high frequencies of use (of a few MHz) while maintaining a large active surface (of the order of mm2). A large active surface can for example correspond to an active surface from 100 μm2 to 10 mm2, for example between 200 μm2 and 9 mm2, between 200 μm2 and 6 mm2, between 200 μm2 and 4 mm2, between 500 μm2 and 2 mm2).
The microbalance thus obtained shows a high-quality factor and thus a good sensitivity (about 50 Hz/ng) while being able to measure a large number of particles with a diameter ranging from 0.1 to 10 μm without saturation (corresponding to mass concentrations ranging from a few ng/m3 to a few 10 μg/m3).
Thus, the microbalance is particularly designed to measure an offset of only a few tens of Hertz around the mechanical oscillation frequency of one to several MHz of the membrane. More particularly, the mechanical oscillation frequency of the membrane is between 1 MHz and 20 MHz, even more particularly the mechanical oscillation frequency of the membrane is between 1 MHz and 20 MHz and the measurement of the offset is a few tens of Hertz around the mechanical oscillation frequency of the membrane 7a, for example about 50 Hz.
The deformation mode according to an in-plane volume mode means that the elastic deformations do not occur locally on the surface but are simultaneous throughout the entire thickness of the membrane 7a. Here the deformations are in-plane, i.e. the deformation is not vertical to the active surface but horizontal. Moreover, the electrostatic actuation allows the electrodes to be positioned not on the active surface of the MEMS membrane 7a, but outside it and act on the thickness of the active surface to deform it.
Thus, these electrodes on the outside alternately cause the membrane 7a to expand and contract in the horizontal directions of the active surface, the membrane with its active surface and thickness moving only in the horizontal directions of the active surface.
Thus, the MEMS membrane 7a is not actuated out of plane (in the direction of the thickness of the active surface).
The sensor 1 may have means for controlling and communicating (wired or radio), electronic or software, allowing the user to acquire, visualize, and exploit data, integrated or remote.
These means allow in particular the integration of the sensor 1 or of a system with a set of sensors 1 in a building air quality control system.
Advantageously, the FP1 separation module includes a selection head, for example a PM10 head. The particle separation module FP1 allows to sort the particles preferably according to their inertia, for example according to their size, and this on several impaction stages.
The particle deposition module FP2 allows particle adhesion. In addition, the particle deposition module is configured to target an area of interest on the MEMS sensor. Thus, the FP2 particle deposition module has a targeted area of interest on the MEMS sensor. In addition, the particle deposition module is configured for particle adhesion by functionalization and/or micro/nano structuring of the MEMS surface. Advantageously, the particle deposition module is configured for the regeneration of the sensor 1 including self-cleaning e.g. by air flow, vibration, temperature.
The FP3 analysis module can be configured to measure the resonance frequency of MEMS sensors before and after particle deposition.
The FP3 analysis module can also be configured to determine the mass of the particles 2 deposited on the MEMS as a function of the frequency shift. Advantageously, this FP3 analysis module allows automated signal processing. This analysis module also allows continuous in-situ analysis.
MEMS 7 microbalances are realized by microfabrication processes in clean room, whose steps are shown in
As shown in
The D layer is made of very low electrically resistive doped Silicon in order to guarantee the electrostatic actuation of the 7a membranes. The H layer is made of highly resistive Silicon to avoid short circuits. The membrane 7a forming the MEMS 7 microbalance is structured in the thickness of the D layer.
A silicon nitride Si3N4 layer of about one hundred nanometer thickness (named N) and then a polycrystalline silicon layer of micrometer thickness (named M) are deposited by LPCVD (Low Pressure Chemical Vapor Deposition) during steps 1 and 2.
A photosensitive resin is deposited on the top surface of the SOI and photolithography is then performed to define the structure of the membrane 7a and electrodes 14 in the resin in steps 3 and 4. At this step the difference between the patterns of the actuating electrodes 14 and the membrane is of the order of two micrometers.
The patterns are then transferred into the polysilicon layer by etching in an RIE (Reactive Ion etching) frame in step 5.
The SOI wafer is then placed in a high-temperature furnace (1100° C.) for several hours in order to oxidize the polysilicon in step 6.
As a result of this oxidation, a silicon oxide almost two microns thick was formed and the openings between the drive patterns and the membrane pattern were reduced to a few hundred nanometers.
During steps 8 and 9, a photolithography, followed by a DRIE etching (“Deep Reactive Ion etching”) is performed to open the oxide layer where the electrical contacts will be deposited.
In a step 10, these patterns are then transferred by RIE etching into the polycrystalline Silicon and then the Silicon Nitride.
In addition, as schematized in step 7, the parameters of steps 1 to 6 as well as those of the D-Silicon DRIE etching have been previously optimized on test plates in order to obtain submicron gap openings.
During steps 11 and 12, a photolithography followed by an Aluminum deposition named “T”, by sputtering and an acetone stripping allow to form the Aluminum contact pads for the electrical signal inputs and outputs.
In step 13, a photolithography is performed on the back side of the SOI to define opening areas under the membrane.
This pattern is transferred into the Silicon oxide of the back side by DRIE etching in a step 14.
The membrane and electrode patterns are transferred into the D-layer by DRIE etching in a step 15.
A final DRIE step on the back side transfers the opening area under the membrane into the H-layer.
The exposed silicon oxide is then dissolved by a hydrofluoric acid (HF) vapor etch in step 16. The membrane is now suspended.
The remaining polysilicon and nitride are finally cleaned by RIE etching in a step 17.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1857827 | Aug 2018 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2019/052011 | 8/30/2019 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/044000 | 3/5/2020 | WO | A |
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| 20100170324 | Mastromatteo et al. | Jul 2010 | A1 |
| Number | Date | Country |
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| International Search Report dated Nov. 20, 2019 in PCT/FR2019/052011 filed on Aug. 30, 2019, 2 pages. |
| French Preliminary Search Report (with English translation of Categories of Cited Documents) dated Jul. 15, 2019 in French Application 1857827 filed on Aug. 30, 2018, 4 pages. |
| Maldonado-Garcia, M. et al., “Chip-Scale Implementation and Cascade Assembly of Particulate Matter Collectors With Embedded Resonany Mass Balances,” IEEE Sensors Journal, vol. 17, No. 6, 2017, pp. 1617-1625, XP011641611. |
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| Number | Date | Country | |
|---|---|---|---|
| 20210255083 A1 | Aug 2021 | US |
