Platform unit for combined sensing of pressure, temperature and humidity
09784631 ยท 2017-10-10
Assignee
Inventors
- Hossam Haick (Haifa, IL)
- Gregory Shuster (Ramat Ishay, IL)
- Meital SEGEV-BAR (Haifa, IL)
- Victoria Kloper (Haifa, IL)
- Sagi Gliksman (Haifa, IL)
Cpc classification
G01N27/121
PHYSICS
G01L19/0092
PHYSICS
B82Y15/00
PERFORMING OPERATIONS; TRANSPORTING
Y10S977/953
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
B82Y15/00
PERFORMING OPERATIONS; TRANSPORTING
G01L19/00
PHYSICS
Abstract
A modular platform unit comprising a plurality of sensors for the combined sensing of pressure, temperature and humidity. In particular, the sensors are composed of a layer of metallic-capped nanoparticles (MCNP) casted on a flexible substrate or a rigid substrate. Integration of the platform unit for artificial or electronic skin applications is disclosed.
Claims
1. A platform unit for detecting a parameter selected from the group consisting of pressure, temperature, humidity and a combination thereof, the platform unit comprising: a plurality of sensors, wherein each of the sensors comprises metallic nanoparticles capped with an organic coating, wherein the plurality of sensors comprise: i) a dual temperature and humidity sensor being deposited on a substantially flexible or rigid substrate; or ii) a dual pressure and humidity sensor being deposited on a substantially flexible substrate; or iii) a dual pressure and temperature sensor being deposited on a substantially flexible substrate; or iv) two sensors, wherein one sensor is a dual pressure and humidity sensor being deposited on a substantially flexible substrate, and the other sensor is a dual pressure and temperature sensor being deposited on a substantially flexible substrate.
2. The platform unit according to claim 1 further comprising at least one of: i) a plurality of electrodes comprising an electrically conductive material, wherein the plurality of electrodes are coupled to each sensor and are used for measuring the signals generated by the sensors; or ii) a detection means comprising a device for measuring changes in resistance, conductance, alternating current (AC), frequency, capacitance, impedance, inductance, mobility, electrical potential, optical property or voltage threshold, or iii) a film, wherein the film is configured to block at least one sensor from generating a signal in response to a change in humidity, or iv) an analyte sensor, wherein the analyte sensor is configured to sense an analyte adsorbed thereon and to generate an electrical signal in response thereto.
3. The platform unit according to claim 1, wherein each sensor is configured in a form selected from the group consisting of a capacitive sensor, a resistive sensor, a chemiresistive sensor, an impedance sensor, and a field effect transistor sensor.
4. The platform unit according to claim 2, wherein the film is characterized by a thickness ranging from about 1 m to about 1000 m, and wherein the film is selected from the group consisting of an epoxy resin, a silicon resin, a polyamide resin, a polyimide resin, a poly(p-xylylene) resin and a combination thereof.
5. The platform unit according to claim 1, wherein the substantially flexible substrate is characterized by widths in the range of about 0.01-10 cm and thicknesses in the range of about 20-500 m.
6. The platform unit according to claim 1, wherein the substantially flexible substrate comprises a polymer.
7. The platform unit according to claim 6, wherein the polymer is selected from the group consisting of polyimide, polyamide, polyimine, polyethylene, polyester, polydimethylsiloxane, polyvinyl chloride, and polystyrene.
8. The platform unit according to claim 1, wherein the substantially rigid substrate is selected from the group consisting of metals, insulators, semiconductors, semimetals, and combinations thereof.
9. The platform unit according to claim 1, wherein the metallic nanoparticles are selected from the group consisting of Au, Ag, Ni, Co, Pt, Pd, Cu, Al, and combinations thereof or wherein the metallic nanoparticles are metallic alloys selected from the group consisting of Au/Ag, Au/Cu, Au/Ag/Cu, Au/Pt, Au/Pd, Au/Ag/Cu/Pd, Pt/Rh, Ni/Co, and Pt/Ni/Fe.
10. The platform unit according to claim 1, wherein the organic coating comprises compounds selected from the group consisting of alkylthiols, arylthiols, alkylarylthiols, alkylthiolates, -functionalized alkanethiolates, arenethiolates, (-mercaptopropyl)tri-methyloxysilane, dialkyl disulfides and combinations and derivatives thereof.
11. The platform unit according to claim 1, wherein the signal generated by each parameter is extracted using pre-measurement calibration, post-measurement calculation or a combination thereof.
12. The platform unit according to claim 1, wherein the plurality of sensors comprise continuous and discontinuous regions of metallic nanoparticles capped with an organic coating.
13. The platform unit according to claim 12, wherein the discontinuous regions comprise voids ranging in size from about 10 nm to about 500 nm.
14. The platform unit according to claim 13, wherein the discontinuous regions comprise between about 3% and about 90% voids.
15. The platform unit according to claim 1, integrated on electronic or artificial skin surface.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
(25) The present invention provides a modular matrix or platform unit for the concurrent detection of pressure, temperature and humidity. In particular, provided herein is a platform comprising MCNP-based sensors which operate at low-power (<0.5V) for multi-functional artificial or electronic skin applications.
(26) The present invention is based in part on the unexpected finding that MCNP-based flexible sensors can possess repeatable measurements of elastic deformation with load sensitivity 0.24 gr. In addition, it is further disclosed that the same sensor technology can be used for sensing environmental conditions with excellent sensitivities for measuring changes in temperature (below 1 C.) and humidity (below 1% RH). It was not previously realized that it is possible to use MCNP-based sensors for concurrent detection of pressure, temperature and humidity on a single platform unit. The ability to detect pressure, temperature and humidity using the same sensor technology integrated on a single platform unit provides a significant advantages over the prior art. The MCNP-based sensors provide repeatable responses even after many bending cycles which render them advantageous for long-term use. Another advantage to the present invention stems from the ability to manufacture micro-scale sensors having high spatial resolution in mass production, thereby enabling their integration in an artificial or electronic skin in well-defined and controllable locations.
(27) In order to achieve independent sensitivities of individual sensors to a single desirable parameter, the following fabrication modulations can be applied:
(28) (i) by using substrates having varying flexibilities and geometric characteristics. For example, by using substantially flexible substrates, the sensor generates an electrical signal mainly attributed to the applied force and not to changes in temperature and humidity. Similarly, by using substantially rigid non-stretching substrates, the sensor generates an electrical signal mainly attributed to changes in temperature and/or humidity and not to pressure.
(29) (ii) by using different organic coatings of the metallic nanoparticles. For example, by using a short di-thiol linker as the capping organic coating, the responses of the sensor to gaseous analytes (including water vapors) can be substantially suppressed. By using a long linker as the capping organic coating, adsorption of various gases can be obtained thereby affording a measurable electrical signal in response to the swelling of the assembly of capped nanoparticles.
(30) (iii) by adding a thin (50 m thick) polymer film, as the top-cover of the sensor. For example, the addition of a top cover can substantially suppress the sensing of humidity and/or volatile organic compounds. Thus, it is contemplated that a thin top-cover film would restrict water vapors from interacting with the metallic nanoparticles capped with an organic coating. The top cover should be thin and possess good heat conduction and low heat capacitance characteristics to assure fast and accurate responses to changes in temperature and/or pressure.
(31) (iv) by modifying the deposition parameters. For example, by using the layer-by-layer deposition technique (Makishima et al., J. Non-Cryst. Sol. 1973, 12, 35-45), control over sensing sensitivities to various analytes can be obtained.
(32) (v) by depositing the NPs at different humidity levels. Thus, it is contemplated that a sensor comprising a film of MCNP which has discontinuous regions provides positive responses upon exposure to various analytes, but negative responses upon exposure to water vapor. By changing the amount of voids in the discontinuous regions, it is possible to control the sensitivity to humidity (water vapors).
(33) (vi) by using pre-measurement calibrations and/or post-measurement algorithmic compensation, an extraction of the data affected by a single parameter (e.g., only temperature) or a plurality of parameters (temperature, humidity and load or strain) can be obtained. For example, two sensors with low sensitivity to load or strain can afford the sensing of changes in temperature and humidity each, while a third flexible sensor affords the sensing of temperature, humidity and load or strain. Post-measurement algorithms can be used to compensate the signals produced by changes in temperature and humidity of the third flexible sensor and enable the extraction or isolation of the signal generated by applied load or strain. In another example, two sensors may sense temperature and humidity simultaneously, having different sensitivities towards each parameter. Then, post-measurement algorithms can be used to calculate the temperature and the relative humidity in an injective manner.
(34) The MCNP-based sensing platform unit of the present invention is particularly suitable for use in artificial or electronic skin technology. The platform unit of the present invention obviates the need for complex integration processes of substantially different devices, each device being sensitive to humidity, temperature, or pressure. The MCNP-based sensing platform unit of the present invention is compatible with cost-effective mass production using various deposition techniques (e.g. spray coating). An additional advantage stems from the wide range of pressures that can be detected and measured by the pressure sensors, which can be achieved by depositing MCNPs on different substrates having various mechanical properties and geometrical characteristic. Moreover, the use of MCNPs pressure sensors on flexible substrates afforded the measurement of very low pressures that have never been detected by the hitherto known pressure sensors (Maenosono et al., J. of Nanopart. Res. 2003, 5, 5-15). Another advantage of the MCNP-based sensors is their ability to operate at low voltage of 0.5V, whereas the hitherto known skin technologies require operation at 5V or more. Such low voltage demands facilitate the integration of the technology presented herein using mobile batteries.
(35) The present invention therefore provides MCNP-based sensing platform unit with excellent temperature and humidity sensitivities which enables the sensing of environmental conditions. The MCNP-based sensing platform unit of the present invention also provides excellent sensitivity to strain which enables its use as touch sensors. The MCNP-based sensing platform unit can be integrated in artificial or electronic skin applications.
(36) According to the principles of the present invention, the platform unit provides the detection of pressure, temperature, and/or humidity. In some embodiments, the platform unit provides the concurrent detection of pressure, temperature, and humidity. The platform unit comprises a plurality of sensors, each sensor comprises a plurality of metallic nanoparticles capped with an organic coating. In certain embodiments, each sensor comprises a plurality of metallic nanoparticles capped with different organic coatings. Suitable metallic nanoparticles within the scope of the present invention include, but are not limited to Au, Ag, Ni, Co, Pt, Pd, Cu, Al, and combinations thereof, including metallic alloys such as, but not limited to Au/Ag, Au/Cu, Au/Ag/Cu, Au/Pt, Au/Pd, Au/Ag/Cu/Pd, Pt/Rh, Ni/Co, and Pt/Ni/Fe. Each possibility represents a separate embodiment of the present invention.
(37) The organic coating of the metallic nanoparticles comprises a monolayer or multilayers of organic molecules. Suitable coating includes, but is not limited to alkylthiols, e.g., alkylthiols with C.sub.3-C.sub.24 chains, arylthiols, alkylarylthiols, alkenyl thiols, alkynyl thiols, cycloalkyl thiols, heterocyclyl thiols, heteroaryl thiols, alkylthiolates, alkenyl thiolates, alkynyl thiolates, cycloalkyl thiolates, heterocyclyl thiolates, heteroaryl thiolates, -functionalized alkanethiolates, arenethiolates, (-mercaptopropyl)tri-methyloxysilane, dialkyl disulfides and combinations thereof. Each possibility represents a separate embodiment of the present invention. Exemplary organic coating includes, but is not limited to 2-nitro-4-trifluoro-methylbenzenethiol, 3-ethoxythiophenol, dodecylamine, and decanethiol. Each possibility represents a separate embodiment of the present invention. In various embodiments, the organic coating is characterized by a thickness ranging from about 1 nm to about 500 nm.
(38) Sensors comprising metallic nanoparticles capped with an organic coating can be synthesized as is known in the art, for example using the two-phase method (Brust et al., J. Chem. Soc. Chem. Commun., 1994, 7, 801) with some modifications (Hostetler et al., Langmuir 1998, 14, 17). In a non-limiting example, AuCl.sub.4.sup. is transferred from aqueous HAuCl.sub.4.xH.sub.2O solution to a toluene solution by the phase-transfer reagent TOAB. After isolating the organic phase, excess thiols are added to the solution. The mole ratio of thiol: HAuCl.sub.4.xH.sub.2O can vary between 1:1 and 10:1, depending on the thiol used. This is performed in order to prepare mono-disperse solution of gold nanoparticles in an average size of about 3-6 nm. Exemplary procedures include, but are not limited to thiol:Au mole ratios of 10:1 and 1:1 for dodecanethiol and butanethiol-capped gold nanoparticics, respectively at an average size of about 5 nm. After vigorous stirring of the solution, aqueous solution of the reducing agent NaBH.sub.4 in large excess is added. The reaction is constantly stirred at room temperature for at least 3 hours to produce a dark brown solution of the thiol-capped Au nanoparticles. The resulting solution is further subjected to solvent removal in a rotary evaporator followed by multiple washings using ethanol and toluene. Gold nanoparticles capped with e.g. 2-mercaptobenzimidazole can be synthesized by the ligand-exchange method from pre-prepared hexanethiol-capped gold nanoparticles. In a typical reaction, excess of thiol, 2-mercaptobenzimidazole, is added to a solution of hexanethiol-capped gold nanoparticles in toluene. The solution is kept under constant stirring for a few days in order to allow as much ligand conversion as possible. The nanoparticles are purified from free-thiol ligands by repeated extractions. The metallic nanoparticles may have any desirable geometry including, but not limited to a cubic, a spherical, and a spheroidal geometry. Each possibility represents a separate embodiment of the present invention.
(39) In some embodiments, the plurality of sensors comprise at least one pressure sensor which is configured to sense pressure applied thereon and to generate an electrical signal in response thereto. According to the principles of the present invention, the pressure sensor is fabricated on a substantially flexible substrate. The term a substantially flexible substrate as used herein refers to a substrate which is configured to elastically deform in response to pressure, wherein said deformation is proportional to the amount of applied pressure. In certain embodiments, the deformation of the substrate generates a change in conformation of the metallic nanoparticles capped with an organic coating. The change in conformation or structural displacement of the metallic nanoparticles capped with an organic coating generates an electrical signal which is proportional to the amount of applied pressure. In other embodiments, the pressure sensor is configured as a strain gauge which translates the mechanical deflection into an electrical signal.
(40) Suitable substantially flexible substrates include stretchable substrates as is known in the art. Exemplary substrates include, but are not limited to polymers which may be polyimide (e.g. Kapton), polyamide, polyimine (e.g. polyethylenimine), polyethylene, polyester (e.g. Mylar, polyethylene terephthalate, polyethylene naphthalate), polydimethylsiloxane, polyvinyl chloride (PVC), polystyrene and the like. Each possibility represents a separate embodiment of the present invention. In one embodiment, the substrate comprises silicon dioxide. In another embodiment, the substrate comprises Si rubber. By modifying the material which forms the substantially flexible substrate from a material having high Young's modulus to a material having low Young's modulus, a change in load sensitivities can be obtained. It is thus contemplated that the substantially flexible substrate enables to control the load sensitivity of the pressure sensor.
(41) The substantially flexible substrate can have any desirable geometry. In rectangular geometries, the width of the substantially flexible substrate ranges between about 0.01-10 cm. The thickness of the substrate can further be tuned, typically in the range of about 20-500 m. The present invention provides the modulation of load sensitivities by changing the width of the sensors' substrate. In addition, the present invention provides the modulation of the gauge factor by adjusting the substrate thickness. Thus, it is contemplated that by modifying the geometrical characteristics of the substrate, desirable load sensitivity and strain gauge factor can be obtained.
(42) The platform unit of the present invention further comprises at least one temperature and/or humidity sensor configured to exhibit a change in conformation of the metallic nanoparticles capped with an organic coating in response to a change in temperature and/or a change in humidity. This change in conformation is then translated into an electrical signal generated in response. Accordingly, the electrical signal is proportional to the change in humidity and/or change in temperature.
(43) In some embodiments, the temperature and/or humidity sensor is fabricated on a substantially rigid or substantially flexible substrate as described herein. Typically, the temperature and/or humidity sensor is fabricated on a substantially rigid substrate. Suitable substantially rigid substrates within the scope of the present invention include, but are not limited to metals, insulators, semiconductors, semimetals, and combinations thereof. Each possibility represents a separate embodiment of the present invention. In exemplary embodiments, the substantially rigid substrate comprises silicon dioxide on a silicon wafer. In another exemplary embodiment, the substantially rigid substrate comprises a substantially rigid polymer. In yet another exemplary embodiment, the substantially rigid substrate comprises indium tin oxide.
(44) In various embodiments, the pressure and/or temperature sensors of the present invention are coated with a film. According to the principles of the present invention, the film is configured to block the pressure and/or temperature sensors from generating a signal in response to a change in humidity. Non-limiting examples of films within the scope of the present invention include epoxy resin films, silicon resin films, polyamide resin films (e.g. nylon and aramid resins), polyimide resin films, poly(p-xylylene) resin films (e.g. Parylenes) and a combination thereof. Each possibility represents a separate embodiment of the present invention. Typically, the film which is configured to block the pressure and/or temperature sensors from generating a signal in response to a change in humidity has thickness in the range of about 1-1000 m.
(45) According to certain aspects and embodiments, the platform unit comprises at least three sensors comprising metallic nanoparticles capped with an organic coating as follows:
(46) (i) a pressure sensor being deposited on a substantially flexible substrate, wherein the pressure sensor is configured to sense pressure applied thereon and to generate an electrical signal in response thereto;
(47) (ii) a temperature sensor being deposited on a substantially rigid substrate, wherein the temperature sensor is configured to exhibit a change in conformation of the metallic nanoparticles capped with an organic coating in response to a change in temperature and generate an electrical signal in response thereto; and
(48) (iii) a humidity sensor being deposited on a substantially rigid substrate, wherein the humidity sensor is configured to exhibit a change in conformation of the metallic nanoparticles capped with an organic coating in response to a change in humidity and generate an electrical signal in response thereto.
(49) In some embodiments, the temperature and humidity sensors are configured to exhibit an independent change in conformation of the metallic nanoparticles capped with an organic coating in response to each of a change in temperature or a change in humidity.
(50) According to certain aspects and embodiments, the humidity sensor comprises continuous and discontinuous regions of conductive metallic nanoparticles capped with an organic coating. In one embodiment, the discontinuous regions comprise voids ranging in size from about 10 nm to about 500 nm, wherein the percentage of voids ranges between about 3% and about 90%.
(51) In certain embodiments, the platform unit comprises a plurality of conducting elements (e.g. electrodes) which are coupled to each sensor, thereby enabling the measurement of the signals generated by the sensors. The conducting elements may include a source and a drain electrode separated from one another by a source-drain gap. The conducting elements may further comprise a gate electrode wherein the electrical signal may be indicative of a certain property of the capped nanoparticles (e.g. a change in conformation of the capped nanoparticles) under the influence of a gate voltage.
(52) The conducing elements may comprise metals such as Au, Ag or Pt electrodes and may further be connected by interconnecting wiring. The distance between adjacent electrodes defines the sensing area. Accordingly, different configurations of the electrodes in the platform unit may be fabricated as is known in the art. Typically, the distance between adjacent electrodes in each sensor ranges between about 0.01-5 mm. In some embodiments, the metallic nanoparticles are casted on a plurality of interdigitated electrodes on a substantially flexible or rigid substrate.
(53) The electrical signal which is generated by the pressure, temperature or humidity sensors may comprise, according to the principles of the present invention any one or more of conductivity, resistance, impedance, capacitance, inductance, or optical properties of the sensors. In some embodiments, the electrical signal is produced by the swelling of the assembly of capped nanoparticles in response to changes in pressure, temperature or humidity. As used herein, the term swelling refers to an increase of the average inter-particle distance in the assembly of capped nanoparticles. In other embodiments, the electrical signal is produced by the aggregation of the assembly of capped nanoparticles in response to changes in pressure, temperature or humidity. As used herein, the term aggregation refers to a decrease of the average inter-particle distance m the assembly of capped nanoparticles.
(54) The sensor signal can be detected by a detection means. Suitable detection means include devices which are susceptible to a change in any one or more of resistance, conductance, alternating current (AC), frequency, capacitance, impedance, inductance, mobility, electrical potential, optical property and voltage threshold. Each possibility represents a separate embodiment of the present invention. In additional embodiments, the detection means includes devices which are susceptible to swelling or aggregation of capped nanoparticles as well as devices which are susceptible to a change in any one or more of optical signal (detected by e.g. spectroscopic ellipsometry), florescence, chemiluminsence, photophorescence, bending, surface acoustic wave, piezoelectricity and the like. Each possibility represents a separate embodiment of the present invention. The measured electrical signals can be displayed on a display or transmitted to a host computer.
(55) The sensors of the present invention can be configured as any one of the various types of electronic devices, including, but not limited to capacitive sensors, resistive sensors, chemiresistive sensors, impedance sensors, field effect transistor sensors, and the like, or combinations thereof. Each possibility represents a separate embodiment of the present invention. In a non-limiting example, the sensors of the present invention are configured as chemiresistive sensors (i.e. chemiresistors). In one embodiment, the sensors of the present invention are not configured as impedance sensors.
(56) Sensors comprising a plurality of metallic nanoparticles capped with an organic coating can be formed on flexible or rigid substrates using a variety of techniques well known in the art. Exemplary techniques include, but are not limited to,
(57) (i) Random deposition from solution by drop casting, spin coating, spray coating and other similar techniques. Each possibility represents a separate embodiment of the present invention.
(58) (ii) Field-enhanced or molecular-interaction-induced deposition from solution. Each possibility represents a separate embodiment of the present invention.
(59) (iii) Langmuir-Blodgett or Langmuir-Schaefer techniques. Each possibility represents a separate embodiment of the present invention.
(60) (iv) Soft lithographic techniques, such as micro-contact printing (mCP), replica molding, micro-molding in capillaries (MIMIC), and micro-transfer molding (mTM). Each possibility represents a separate embodiment of the present invention.
(61) (v) Various combinations of Langmuir-Blodgett or Langmuir-Schaefer methods with soft lithographic techniques. Each possibility represents a separate embodiment of the present invention.
(62) (vi) Printing on solid-state or flexible substrates using an inject printer designated for printed electronics.
(63) The present invention further encompasses sensors having dual sensing sensitivities, such as a dual temperature and pressure sensor, a dual temperature and humidity sensor, and/or a dual pressure and humidity sensor. Each possibility represents a separate embodiment of the present invention.
(64) A non-limiting example of a platform unit which comprises dual sensors includes a platform unit comprising three sensors, wherein two sensors are dual temperature and humidity sensors being deposited on a substantially flexible substrate, and a third pressure sensor being deposited on a substantially flexible substrate. It is contemplated that the choice of substrate is used to alter the sensitivity of the sensors to changes in load, temperature and/or humidity. An additional non-limiting example of a platform unit which comprises dual sensors includes a platform unit comprising two sensors, wherein one sensor is a dual pressure and humidity sensor being deposited on a substantially flexible substrate, and the other sensor is a pressure and temperature sensor being deposited on a substantially flexible substrate. One of skill in the art readily understands that a signal generated by each parameter (temperature, humidity or pressure) is extracted using pre-measurement calibration, post-measurement calculation or a combination thereof.
(65) The arrangement of the plurality of sensors in the platform unit can be performed as is known in the art. Non-limiting arrangement includes a matrix of sensors (rows and columns) comprising a plurality of sensors, for example between 2 and 20 sensors, wherein each sensor independently generates an electrical signal in response to pressure, temperature and/or humidity. Each sensor comprises metallic nanoparticles capped with a different or similar organic coating and a different or similar substrate.
(66) According to certain aspects and embodiments, the sensors of the present invention are coated with a film. In some embodiments, the film provides the protection of the metallic nanoparticles capped with an organic coating from physical damage, scratching and oxidation. The coating can be performed by processes well known in the art such as, but not limited to, spin coating and the like. The film could be permeable to water or not, depending on the required application. The film could conduct heat or isolate the sensor from external temperature changes. In some embodiments, the film comprises polycyclic aromatic hydrocarbons (PAHs). In other embodiments, the film comprises carbon coatings, nitrogenated carbon coatings, thermoplastic resins, silicate coatings or any other suitable coating known in the art. Typically, the film possesses a thickness which ranges from about 0.001 to about 10 m.
(67) According to various aspects and embodiments, the platform unit further provides the detection of a volatile organic compound (an analyte) using an analyte sensor, wherein the analyte sensor is configured to sense an analyte adsorbed thereon and to generate an electrical signal in response thereto. Thus, it is contemplated that the platform unit would further provide the detection of the presence and concentration of volatile organic compounds in the surrounding environment. In some embodiments, the volatile organic compounds are biomarkers indicative of a disease or disorder in a subject.
(68) The platform unit of the present invention may be used for artificial and/or electronic skin applications which require the production of large-scale sensor arrays that can sense load, relative humidity and temperature with high resolution and short response times. Artificial and/or electronic skin may be integrated in medical prosthesis and robotics industries. Additional applications include, but are not limited to, use by individuals in order to keep track of loads they carry (e.g. harbor employees) and measure their physical response including body temperature and humidity; and use to cover engines of cars and planes which can be configured to set alarms once excess temperature or pressure are being detected and/or early formation of cracks initiates.
(69) As used herein and in the appended claims the singular forms a, an, and the include plural references unless the content clearly dictates otherwise. Thus, for example, reference to an organic coating includes a plurality of such organic coatings and equivalents thereof known to those skilled in the art, and so forth. It should be noted that the term and or the term or is generally employed in its sense including and/or unless the content clearly dictates otherwise.
(70) The following examples are presented in order to more fully illustrate some embodiments of the invention. They should, in no way be construed, however, as limiting the broad scope of the invention. One skilled in the art can readily devise many variations and modifications of the principles disclosed herein without departing from the scope of the invention.
EXAMPLES
(71) Materials and Methods
(72) Synthesis of MCNPs:
(73) Gold (III) chloride trihydrate (HAuCl.sub.4.3H.sub.2O), tetraoctylammonium bromide (TOAB), sodium borohydride, 3-ethoxythiophenol (ETP), decanethiol (DT) and 2-nitro-4-trifluoro-methylbenzenethiol (NTMBT) were purchased from Sigma-Aldrich. All reagents were of analytical grade and were used as received. Spherical gold nanoparticles (AuNPs; 3-6 nm in diameter) were synthesized as described in Peng et al., Nature Nanotech. 2009, 4, 669-673; and Dovgolevsky et al., J. Phys. Chem. C. 2010, 114, 14042-14049; the content of each of which is hereby incorporated in its entirety. Briefly, a solution of HAuCl.sub.4 was added to a stirred solution of TOAB in toluene. After 10 min stirring, the lower aqueous phase was removed. Organic ligands and sodium borohydride were subsequently added to the toluene phase. After 3 hours at ice temperature, the lower aqueous phase was removed and the toluene phase was subsequently evaporated by rotary evaporation. After first washing with cold ethanol, the solution was kept at 5 C. for 18 hours until complete immersion was achieved. The dark brown precipitate was filtered off and washed with ethanol.
(74) Sensor Fabrication:
(75) Electrodes were deposited on different isolating substrates (Table 1). The electrodes were prepared using silver paste (Mouser Electronics). The spacing between the electrodes was typically 1 mm in all experiments that examined the substrate effect on the load sensitivity. Similar printed electrodes with variable spacing of 0.5, 1 and 3 mm were used in order to examine the effect of spacing between the electrodes. Stretching was performed on dog bone samples cut from the same substrate as in the bending experiments. Electrodes were prepared in a similar manner using silver paste with 1 mm spacing between the electrodes. The substrates were obtained from DuPont (GADOT as distributers). Flexible sensors were prepared by casting 2 l of MCNPs in solution on top of the flexible substrates/electrodes.
(76) Morphology Characterization of the MCNP Layers:
(77) The microstructure and morphology of the MCNP films were characterized by field emission high-resolution scanning electron microscopy (Carl Zeiss Ultra Plus FE-HRSEM). The FE-HRSEM analysis was performed using two main detectors: secondary electrons (SE) detector and back scattered electrons (BSE) detector. The SE detector provides high-resolution imaging of the surface. The BSE detector provides image contrast as a function of elemental composition as well as surface topography.
(78) The morphology of the MCNP films was additionally examined by a tapping mode atomic force microscope (AFM) (Dimension 3100 with Nanoscope IIIa controller, Veeco Instruments Inc.) that is equipped with a 100100 m.sup.2 scanner. Silicon cantilevers with a normal resonance frequency of 160 kHz and spring constants of 5 N/m (NSCl.sub.4/AlBs, MikroMasch, Estonia) were used. All images were captured with a scan rate of 1-2 Hz and a pixel resolution of 512512.
(79) The Set-Up of Bending Experiments:
(80) A MARK 10 ESM301 motorized test stand was used to apply a constant strain of 1.5 mm/sec. For bending setup (
(81) The Set-Up of Stretching Experiments:
(82) Strain/force was applied between 2 metal grips on a dog bone sample that is illustrated in
(83) Preparation of the Integrated Pressure/Temperature/Humidity Sensors:
(84) Humidity or temperature sensors based on MCNP layers on SiO.sub.2 substrate were prepared by drop casting aliquots of MCNP solution on interdigitated electrodes consisting of 24 pairs of Au electrodes (5 m width and 25 m spacing between adjacent electrodes) on a silicon wafer with a 1000 nm SiO.sub.2 film. Between those sensors, a flexible ETP-MCNP layer on PET substrate was placed (
(85) The Set-Up of Evaluation of Temperature and Relative Humidity Sensing Experiments:
(86) Twenty sensors were mounted on a custom PTFE circuit board. The board was mounted into a stainless steel test chamber with a volume of less than 300 cm.sup.3. For controlling the relative humidity levels (5-60% RH), purified dry nitrogen (99.9999%) from a commercial nitrogen generator (N-30, On Site Gas Systems, USA) equipped with a nitrogen purifier was used as a carrier gas. The dry nitrogen was mixed with humidified air generated by the system's humidifier module. Controlled temperatures were produced by a custom-made temperature controller. The sensing experiments were performed by monitoring the response of the MCNP and environmental sensors (RH, temperature) to different relative humidity and temperature levels generated by the system.
(87) During ambient sensing experiments (Tables 3-4 and
(88) MCNP-Based Pressure Sensor:
(89) The sensors were prepared on polyethylene (PE) substrates. Ten pairs of 4.5 mm wide, interdigitated (ID) electrodes with an inter-electrode spacing of 100 m were formed on the substrates by evaporation of 20 nm/200 nm Ti/Au layer through a shadow mask. Chemiresistors were prepared by drop casting aliquots of representative MCNP solutions. A homemade three-point bending system was used in a probe station. Under applied force, the beam that is subjected to the three-point bending test is bent downwards as schematically illustrated in
(90) The moment of inertia (I) for a rectangular sample (
(91)
(92) The surface area (A):
(93) A=20 mm.sup.2
(94) The applied pressure (P):
(95)
(96) Where E is the Young's modulus and is the deflection of the center of the sample. For example, when using polyethylene as a substrate, .sub.minimum=0.075 mm, the Young's modulus is 500 MPa, and the pressure for each deflection value:
P=0.032.Math.
(97) Using the minimal measured deflection value of 0.075 mm, the sensor was subjected to a load of 0.24 gr:
P(=0.075 mm)=2.4.Math.10.sup.3N=0.24 gr
(98) and the resulting calculated stress () is:
(99)
(100) The probe station, connected to a device analyzer (Agilent B1500A), was used to collect the electrical signals of the MCNP-based pressure sensor during bending and stretching. Resistance as a function of time was measured under constant voltage of 0.5V.
Example 1: Sensing Temperatures and Humidity
(101) The possibility to integrate temperature and humidity sensing capabilities within the MCNP-based touch platforms was examined. For this purpose, nitro-4-trifluoro-methylbenzenethiol (NTMBT) MCNP sensors were placed in a vacuum chamber with a controllable environment. The temperature or relative humidity (RH) was altered in a stepwise manner, and the corresponding R/R.sub.b was monitored.
(102)
Example 2: The Effect of Stretching and Bending on the Flexible MCNP Sensors
(103) Pressure sensors of gold nanoparticles capped with 3-ethoxythiophenol ligands (ETP-MCNP) on flexible polyethylene terephthalate (PET) substrates were examined by a three-point bending test, under bending and stretching conditions. All experiments were performed at the room temperatures of 20 C.1 C. and relative humidity (RH) levels of 50%3%.
(104) Similar results were obtained using gold nanoparticles capped with decanethiol (DT-MCNP) on flexible polyethylene (PE) substrate. The DT MCNP film was subjected to bending and stretching.
(105) To estimate the range of load sensitivities, similar measurements were performed on several substrates with different elastic properties. Three-point bending calculations were performed on several substrates with different elastic properties (different Young modulus) as follows: PDMS (Young's modulus of 360-870 KPa; PE (Young's modulus of 500 MPa); SiO.sub.2 (glass; Young's modulus of 70 GPa); and Si rubber (Young's modulus of 75 KPa). For minimal load estimation, using the lowest measured deflection value of 0.075 mm, the sensor was subjected to a load of 0.24 gr on a PE substrate. To achieve the same level of deflection (the deflection is proportional to the strain and the change of resistance) when using PDMS as a substrate under the same experimental conditions, the sensor would have to be subjected to a load of only 0.24 mg and thus a lower detection limit would be achieved. When using glass as the substrate, measuring of higher values of stress compared to a PE substrate while maintaining similar strain levels can be obtained. Hence, using a deflection value of 0.525 mm, a DT-MCNP-SiO.sub.2 platform would need to be subjected to a load of 238 gr to achieve similar deflection to that achieved when the DT-MCNP-PE platform was subjected to a load of 1.7 gr.
(106) When using PDMS as a substrate, the sensor was sensitive to a load of 0.24 mg. DT-MCNP on glass (SiO.sub.2) provided sensitivities of higher loads (238 gr) than the sensitivities obtained for DT-MCNP on PE (1.7 gr). When Si rubber was used as the substrate (DT-MCNP-Si rubber platform), the calculated limit of detection was lower by eight-fold in comparison to the DT MCNP PE platform.
(107) A tunable load sensor based on ETP-MCNP layer casted on a flexible substrate is presented. The low standard deviations and the high signal-to-noise ratios of the signal's output for repeated load in
Example 3: The Effect of the Substrate on the MCNP Layer Morphology and on the Related Sensing Properties
(108) The relative response of the sensors is directly proportional to the deflection (for a certain bending set-up). Accordingly, when introducing larger deflections, the responses of the flexible sensors increase. Since large deflections can cause irreversible changes both to the flexible substrate as well as to the MCNP layer, a range of load sensitivities is required. In this manner, high loads are measurable using thick substrates having high Young's modulus and small loads are measurable using thin substrates having low Young's modulus.
(109) The relation between the properties of the substrate and the MCNP-based load sensors was explored by deposition of ETP-MCNP films on: (i) substrates having similar composition (e.g., the same polymer) but different thicknesses; and (ii) substrates having different compositions (e.g., different polymers) but similar thicknesses (e.g., 50 m thick substrates). The flexible substrates and their properties are listed in Table 1.
(110) TABLE-US-00001 TABLE 1 Fabricated MCNP/substrate sensors Young's Substrate modulus thickness Load Substrate (MPa) (m) Sensitivity.sup.(a) PVC 200 2200 200 0.04 0.003 Kapton 50 2500 50 0.23 0.03 Kapton 127 2500 127 0.04 0.014 Kapton b. 131 4430 131 0.03 0.008 PET 125 4200 125 0.01 0.005 Mylar 36 4100 36 0.31 0.036 Mylar 50 4100 50 0.07 0.019 .sup.(a)load sensitivity: relative change of resistance per unit change in the load.
(111) The surface morphology of ETP-MCNP films on different substrates was studied by field emission high-resolution scanning electron microscopy (FE-HRSEM) and atomic force microscopy (AFM).
(112)
(113)
(114)
(115) where b is the substrate's width (which was substantially similar in all substrates used) and h is the substrate's thickness. The relation between the sensor's sensitivity, load, and the substrate parameters is provided by the following equation:
(116)
(117) where P is the load change.
(118) To estimate the range of the load sensitivities, two types of sensors were examined under various loads: (i) an ETP-MCNP film deposited on Mylar 36 (load sensitivity=0.31) subjected to 200 mg-1 gr loads; and (ii) an ETP-MCNP film deposited on PET 125 (load sensitivity=0.01) subjected to 200 mg-10 gr loads.
(119) Stretching properties of the ETP-MCNP-based sensors were tested. Dog bone samples (
=E
(120) where is the applied force divided by the cross sectional area, S is the strain in the sample and E is the Young's modulus. In this setup, the width of all of the sensors was substantially equal. Therefore, the load sensitivity is expressed by:
(121)
(122) where h is the substrate thickness.
(123) Hence, there is a direct link between the substrate's properties and the measured load sensitivities, both in bending setup (
Example 4: Fine Tuning of the Sensing Properties of the Flexible MCNP Sensors
(124) For determining the factors which control the load sensitivity of the sensors, additional parameters were examined as follows: (i) electrode spacing; (ii) substrate related parameters (e.g. width); and (iii) MCNP film related parameters (e.g. capping ligand). In order to determine the electrodes' spacing effect, ETP-MCNP layer was casted on electrode spacing ranging from 0.5-3 mm. The error bars are the standard deviation of 3 tested sensors for specific electrode spacing.
(125)
(126) An additional factor which controls the sensitivity of MCNP-based flexible sensors is provided by changing the capping MCNP layer. The MCNPs' organic ligands determine the chemical bonds' type and strength between neighboring MCNPs thereby affecting the load sensitivity. The tunneling decay constant which determines the change in resistance is also affected by the capping ligands.
(127) Hence, by adjusting the substrate width and/or changing the capping ligand in the MCNP sensor, a control over the load sensitivities can be obtained.
Example 5: Flexible MCNP Sensors as Strain Gauges
(128)
(129) TABLE-US-00002 TABLE 2 Gauge sensors Nanoparticle diameter (nm) GF Substrate 14 35-41 PET.sup.(a)125 m.sup.(c) 18 135 PET.sup.(a) 125 m.sup.(d) 4 10-20 LDPE.sup.(b) 560 m.sup.(e) 18 100 photoresist 140 m.sup.(f) 2-5 50-250 (substrate depended) Variety of substrates .sup.(a)PET = Polyethylene terephthalate .sup.(b)LDPE = Low-density polyethylene .sup.(c)Farcau et al., ACS Nano 2011, 5, 7137-7143 .sup.(d)Tsung-Ching et al, J. Disp. Tech. 2009, 5, 206-215 .sup.(e)Vossmeyer et al., Adv. Funct. Mater. 2008, 18, 1611-1616 .sup.(f)Herrmann et al., Appl. Phys. Lett. 2007, 91, 183105
(130) Demonstrated herein is the use of the sensors and matrix of the present invention as highly sensitive strain gauges. Commercial strain gauges have typical gauge factor of 2. MCNP Strain gauges have adjustable gauge factor that is affected and can be controlled by the substrate thickness.
Example 6: Fatigue Properties of Flexible MCNP Sensors
(131) The fatigue properties over a large number of bending cycles were tested using three sensors on flexible Kapton 127 substrate and ETP-MCNP as the sensing layer. The sensors were subjected to strains of 0.3% for 10,000 cycles. In one of the sensors, the baseline resistances changed dramatically and, therefore, the sensor was excluded. The other two sensors (S1 and S2) showed a drift in baseline resistance upon increasing the number of bending cycles (
Example 7: Temperature and Humidity Sensing with Flexible MCNP Sensors
(132) The possibility to integrate temperature and relative humidity (RH) sensing capabilities using the MCNP-based touch platforms was examined on an ETP-MCNP sensor mounted on a PET substrate. In order to test the sensor's responses to temperature and RH, the sensor was placed in a vacuum chamber having a controllable environment. The temperature and RH were altered separately, and the corresponding R/R.sub.b was monitored.
(133) Hence, it is contemplated that the sensitivity of the ETP-MCNP-based sensor is high enough to detect temperature fluctuations with a resolution less than 1 C. and humidity fluctuations with resolution of 1% RH using a linear approximation of the sensor relative response. The sensors and platform of the present invention could therefore be used e.g. as a human body thermometer or sense a heat source in the vicinity of an artificial or electronic skin, without the need for touching the object.
Example 8: Touch Sensing Application
(134) A demonstration of the ability of the MCNP sensors as touch sensors was performed by encoding letters using Morse code. Morse code is a combination of long and short pulses (lines and dots) that encode the entire alphabet and 10 digits (
(135) It is therefore contemplated that load sensitivity can be adjusted by using different substrates. Accordingly, it is possible to design sensor matrices that are sensitive to different load ranges (e.g. suitable for small children as well as adults). Additional applications include intravascular neurosurgery where the sensing of load lower than 200 mg are required, a seat-belt sensor having small load sensitivity to transduce at loads larger than 1,000 Kg, or scoliosis surgery where high-load stress sensors are required.
(136) Most touch panels today are based on an on/off sensing mechanisms were the devices are able to sense applied load but with no ability to determine the load (Walker, J. Soc. Info. Disp. 2012, 20, 413-440). The platform unit of the present invention has the capability of not merely to sense touch but also to sense the load magnitude. Using a variety of substrates allows tuning the sensing properties to specific load ranges that are required for a specific application.
Example 9: MCNP-Based Sensing Platforms for Integrated Measurement of Pressure, Temperature and Humidity
(137) Sensing various parameters (e.g., pressure, temperature, humidity) from a complex sample using a single flexible sensing platform is demonstrated herein. A prototype based on MCNP technology was prepared and its abilities to measure the surrounding temperature, relative humidity and applied load were estimated. Different substrates were used in order to eliminate the load sensing from part of the sensors, and different capping ligands were chosen to isolate the sensing of relative humidity or temperature. Two sensors were fabricated by casting ETP-MCNP and NTMBT-MCNP on silicon dioxide with evaporated interdigitated gold electrode. A third sensor was fabricated by casting ETP-MCNPs on a PET substrate with 1 mm electrodes spacing as illustrated in
(138) Temperature and humidity were calculated using the inflexible sensors. For sensing relative humidity, a perforated NTMBT-MCNP film was used as described in Segev-Bar et al., J. Phys. Chem. C. 2012, 116, 15361-15368; the content of which is hereby incorporated in its entirety. This sensor has a large negative response (up to 80%) to increasing levels of RH due to ionization mechanism. As can be seen in
(139) The prototype platform was exposed to different temperature and relative humidity cycles controlled by air conditioning in a room. The relative humidity range was 33-60% and the temperature range was 15-22 C. The relative humidity was modeled by a linear fit in
(140) TABLE-US-00003 TABLE 3 Summary of the accuracy for measuring temperature and RH using S1 and S2 Temperature RH average Cycle average error (%) error (%) 1 17.7 2.6 5.8 6.9 2 2.3 1.2 20 5.7 3 0.7 0.6 10.7 9.8 4 8 1.4 5.8 6 5 9.4 1.5 6.6 7.3 6 10.2 1.3 7.8 6.2
(141) For assessing the performance of the prototype platform in sensing load, an unknown load was applied on the flexible ETP-MCNP sensor. For this purpose an algorithm that accounts for the temperature, RH and load is required. In general, the change in resistance of a given sensor is a factor of three parameters: temperature, RH and load. The effect of each parameter may be linear or non-linear. However, as disclosed herein, it is possible to model and measure a sensor's resistance due to changes in RH and temperature under a given load. To demonstrate the ability to easily model the effect of RH and temperature, several experiments were performed. The correlation between temperature and RH on the sensor's resistance was established by exposing the sensor to a range of temperatures (23-38 C.) at 2 different constant RH conditions (
R=R.sub.baseline+R.sub.RH.Math.RH+R.sub.T.Math.T
where R is the measured resistance of the sensor; R.sub.RH is the change in resistance per unity change in the relative humidity; R.sub.T is the change in resistance per unity change in the temperature; and R.sub.baseline is the extrapolated resistance under zero temperature and RH. A linear model was used for simplicity. Based on this equation, the response of the flexible ETP-MCNP sensor can be described as a plane in the resistancetemperatureRH space.
(142) The three-sensor-based prototype was measured under changing environmental conditions as mentioned above. The flexible ETP-MCNP sensor was examined under different loads. The response of the flexible ETP-MCNP sensor to temperature (R.sub.T) and relative humidity (R.sub.RH) was different for different loads, and calculated using a solver script in Microsoft. The input parameters that were used are: the different environmental conditions (temperature and relative humidity) and the corresponding resistance of the flexible ETP-MCNP sensor.
(143)
(144) TABLE-US-00004 TABLE 4 Calculated and applied loads on an ETP-MCNP sensor deposited on a PET substrate. Applied Calculated load Load 18.7 C., 47% RH 19.7 C., 45% RH 21.4 C., 43.5% RH 3 gr 2.42 gr 2.8 gr 3.07 gr 6 gr 6.7 gr 6.68 gr 6.08 gr
(145) The accuracy of the model was estimated by measuring the load sensitivity of the ETP-MCNP sensor on PET substrate at specific temperatures and RHs, calculating the relative response of the sensor at these environmental conditions based on the plans that are presented in
(146) The matrix prototype presented herein uses different MCNP on inflexible substrate in order to sense temperature and humidity in an un-conjugated manner (were a single sensor senses only either temperature or relative humidity). A post measurement algorithm was used for the flexible ETP-MCNP sensor in order to isolate load sensing from other parameters (temperature and humidity). When load was applied, the enlarging distance between the nanoparticles changed the surface coverage which resulted in a change in morphology. These changes affect the MCNP sensor response. In instances where the effect of temperature and RH on resistance is not linear, it is possible to model the correlation, and draw representative non-linear planes that would enable the measurements of the desired parameter.
Example 10: Integration of Load, Temperature and RH Sensors (3 in 1) Via Layer-by-Layer Deposition
(147) Gold nanoparticles coated with dodecylamine (DA-GNPs) were deposited via the layer-by-layer (LBL) technique (Joseph et al., J. Phys. Chem. C. 2007, 111, 12855-12859; and Vossmeyer et al., Adv. Funct. Mater. 2008, 18, 1611-1616) on a Kapton substrate having two electrode pairs with different shapes and spaces (S1 and S2). S1 had an interdigitated structure of 10 pairs of Au electrodes (100 m width and 100 m spacing between adjacent electrodes). S2 and S3 had 2 electrodes with 100 m spacing between them. The use of different pairs of electrodes resulted in different baseline resistances for S1 and S2 (150 K for S1 and 4100 K for S2). Hence, by fabricating the environmental sensors using different electrode structures, different responses to temperature and humidity are obtained. S3 was placed facing down towards the table assuring partial shielding from the environment. A small window engraved into the substrate allowed physical sinking when the sensor was pressed towards the table (
R.sub.i=R.sub.ibaseline+R.sub.iRH.Math.RH+R.sub.iT.Math.T
where R.sub.i is the measured resistance of sensor i under certain RH and temperature (T) conditions, and R.sub.ibaseline is the extrapolated resistance under zero temperature and RH. Based on the two sensors that create different planes in the resistancetemperatureRH space, the temperature and the relative humidity was calculated in an injective manner (
(148) TABLE-US-00005 TABLE 5 Summary of the model's accuracy for temperature and RH sensing with S1 and S2 Measured Calculated temperature temperature % Measured Calculated Deviation ( C.) ( C.) deviation RH (%) RH (%) (%) 22.1 22 0.5 59.2 58.6 1 23.7 23.3 1.7 82 84.7 3.3 25.3 25.4 0.4 83 83.1 0.1
(149) In order to test the accuracy of the received model, three additional points of resistance under different environmental conditions were measured by an external sensor and calculated through the fitted equations. The results are presented in Table 5. The middle sensor facing down (S3) was less sensitive to the variations in humidity and temperature, where the effect on the resistance was less than 1% throughout the entire experiment. In comparison, when applying pressures of about 15 KPa, the response due to bending of the substrate was about 2% (
(150) Hence, by using an array of 3 sensors in which the load sensor is protected from environmental effects and the other two sensors are protected from mechanical deflection, multi-parametric sensing can be obtained. These results demonstrate the possibility of producing and integrating temperature and humidity sensors as part of an artificial or electronic skin application based on MCNPs. Thus, it is possible to use a single (or similar) MCNP chemistry with various substrate structures/designs to achieve multi-parametric sensing such as temperature, relative humidity and load, on the same platform.
(151) It is appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the present invention includes both combinations and sub-combinations of various features described hereinabove as well as variations and modifications. Therefore, the invention is not to be constructed as restricted to the particularly described embodiments, and the scope and concept of the invention will be more readily understood by references to the claims, which follow.