EP3472607A2 - Dispositifs à effet de champ dont la grille est constituée par un fluide polaire - Google Patents

Dispositifs à effet de champ dont la grille est constituée par un fluide polaire

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Publication number
EP3472607A2
EP3472607A2 EP17812823.7A EP17812823A EP3472607A2 EP 3472607 A2 EP3472607 A2 EP 3472607A2 EP 17812823 A EP17812823 A EP 17812823A EP 3472607 A2 EP3472607 A2 EP 3472607A2
Authority
EP
European Patent Office
Prior art keywords
field effect
effect transistor
polar fluid
nanoscale material
polar
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17812823.7A
Other languages
German (de)
English (en)
Other versions
EP3472607A4 (fr
Inventor
Rajatesch R. GUDIBANDE
Saurabh RADHAKRISHNAN
Antoine GALAND
Meet VORA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Graphwear Technologies Inc
Original Assignee
Graphwear Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Graphwear Technologies Inc filed Critical Graphwear Technologies Inc
Publication of EP3472607A2 publication Critical patent/EP3472607A2/fr
Publication of EP3472607A4 publication Critical patent/EP3472607A4/fr
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
    • G01N33/54353—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals with ligand attached to the carrier via a chemical coupling agent
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4146—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS involving nanosized elements, e.g. nanotubes, nanowires
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing

Definitions

  • the invention disclosed herein generally relates to the design, making and applications of nanoscale field effect transistors (NFETs) gated by polar fluids, in particular graphene field effect transistors (GFETs).
  • NFETs nanoscale field effect transistors
  • GFETs graphene field effect transistors
  • the present disclosure also relates generally to chemical and biological sensing using field effect transistors and more particularly to biochemical sensing using field effect transistors with a bio-chemically sensitive channel involving graphene.
  • the field-effect transistor is a transistor that uses an electric field to control the electrical behavior of the device.
  • a FET has three terminals (e.g., source, drain, and gate) and an active channel. Though the active channel, e.g., formed by a semi- conductive material, charge carriers (electrons or holes) flow from the source to the drain.
  • Source (S) is where the carriers enter the channel.
  • Drain (D) is where the carriers leave the channel.
  • Drain-to-source voltage is VDS, and source to drain current is IDS.
  • Gate (G) modulates the channel conductivity by applying a gate voltage (VG) to control a current between source and drain.
  • Nanoscale field effect transistors such as graphene field effect transistors (GFETs) are widely used in numerous applications such as in bioprobes, implants, and etc.
  • a field effect transistor comprises: a drain electrode; a drain electrode; a source electrode; an electrically insulating substrate; a nanoscale material layer arranged on the substrate, the nanoscale material layer partially defining an electrically conducting and chemically sensitive channel, the nanoscale material layer and the channel extending between and being electrically connected to the drain electrode and source electrode; and a polar fluid induced gate terminal created by a polar fluid exposed to the nanoscale material layer.
  • the polar fluid comprises the target analyte.
  • the polar fluid has a charge concentration sufficient to induce a polar fluid gate voltage that optimizes the gate voltage versus channel current characteristics of the field effect transistor in response to the target analyte
  • a constant current or a constant voltage is applied between the source and drain electrodes, provided by a constant current source or a constant voltage source.
  • the nanoscale material comprises graphene, CNTs, MoS2, boron nitride, metal dichalcogenides, phosphorene, nanoparticles, quantum dots, fullerene, 2D nanoscale material, 3D nanoscale material, 0D nanoscale material, ID nanoscale material or any combination thereof.
  • the polar fluid comprises a solution with polar molecules , a gas with polar molecules, a target sensing analyte, or combinations thereof.
  • the polar fluid comprises sweat, breath, saliva, earwax, urine, semen, blood plasma, a bio-fluid, a chemical fluid, an air sample, a gas sample, or a combination thereof.
  • the target analyte comprises an electrolyte, glucose, lactic acid, IL6, a cytokine, HER2, Cortisol, ZAG, cholesterol, vitamins, a protein, a drug molecule, a metabolite, a peptides, an amino acid, a DNA, an RNA, an aptamer, an enzyme, a biomolecule, a chemical molecule, a synthetic molecule, or combinations thereof.
  • the field effect transistor further comprises: a receptor layer deposited on the nanoscale material layer, wherein the receptor layer comprises receptors targeting the target analyte.
  • the receptors comprise pyrene boronic acid (PBA), pyrene N-hydroxysuccinimide ester (Pyrene- HS), organic chemicals, aromatic molecules, cyclic molecules, enzymes, proteins, antibodies, viruses, single stranded DNAs (ssDNAs), aptamers, inorganic materials, synthetic molecules, biological molecules.
  • the field effect transistor further comprises: a back polymer layer under the nanoscale material layer to provide support for additional mechanical, electrical, chemical, biological functionality or combinations thereof .
  • the back polymer layer comprises: carbon polymers, bio polymers, PMMA, PDMS, flexible glass, nanoscale materials, silica gel, silicone, inks, printed polymers or any combination thereof.
  • a method for sensing a target analyte in a polar fluid comprises: exposing the polar fluid sample to a field effect transistor, where the field effect transistor comprises: a drain electrode; a source electrode; an electrically insulating substrate; a nanoscale material layer arranged on the substrate, the nanoscale material layer at least partially defining an electrically conducting and chemically sensitive channel, the nanoscale material layer and the channel extending between and being electrically connected to the drain electrode and source electrode; and a polar fluid induced gate terminal created by the polar fluid exposed to the nanoscale material layer, wherein the polar fluid comprises the target analyte and has charge concentration sufficient to induce a polar fluid gate voltage that optimize the gate voltage versus channel current characteristics of the field effect transistor for detecting the analyte; measuring a first source-drain voltage at a first time point and a second source-drain voltage at a second and subsequent time point; and determining a concentration of the target analyt
  • the nanoscale material comprises graphene, CNTs, MoS2, boron nitride, metal dichalcogenides, phosphorene, nanoparticles, quantum dots, fullerene, 2D nanoscale material, 3D nanoscale material, 0D nanoscale material, ID nanoscale material or any combination thereof.
  • the field effect transistor is functionalized with a receptor layer deposited on the nanoscale material layer, and wherein the receptor layer comprises receptors targeting the target analyte.
  • the receptors comprise pyrene boronic acid (PBA), pyrene N-hydroxysuccinimide ester (Pyrene-NHS), organic chemicals, aromatic molecules, cyclic molecules, enzymes, proteins, antibodies, viruses, single stranded DNAs (ssDNAs), aptamers, inorganic materials, synthetic molecules, biological molecules.
  • the target analyte comprises an electrolyte, glucose, lactic acid, IL6, a cytokine, HER2, Cortisol, ZAG, cholesterol, vitamins, a protein, a drug molecule, a metabolite, a peptides, an amino acid, a DNA, an RNA, an aptamer, an enzyme, a biomolecule, a chemical molecule, a synthetic molecule, or combinations thereof.
  • the polar fluid comprises a solution with polar molecules , gas with polar molecules, target sensing analyte or combinations thereof.
  • the method further comprises calculating a fractional change between the first and second source-drain voltages.
  • the method further comprises: applying a constant current between the source and drain electrodes of the field effect transistor.
  • the method further comprises: applying a constant voltage between the source and drain electrodes of the field effect transistor.
  • the polar fluid comprises sweat, breath, saliva, earwax, urine, semen, blood plasma, a bio-fluid, a chemical fluid, an air sample, a gas sample, or a combination thereof.
  • the method further comprises: a back polymer layer under the nanoscale material layer to provide support for additional mechanical, electrical, chemical, biological functionality or combinations thereof .
  • the back polymer layer comprises: carbon polymers, bio polymers, PMMA, PDMS, flexible glass, nanoscale materials, silica gel, silicone, inks, printed polymers or any combination thereof.
  • a system comprising: a field effect transistor;
  • a constant current source or a constant voltage source electrically connected with the field effect transistor comprises: a drain electrode; a source electrode; an electrically insulating substrate; a nanoscale material layer arranged on the substrate, the nanoscale material layer partially defining an electrically conducting and chemically sensitive channel, the nanoscale material layer and the channel extending between and being electrically connected to the drain electrode and source electrode; and a polar fluid induced gate terminal created by a polar fluid exposed to the nanoscale material layer.
  • the polar fluid comprises the target analyte.
  • the polar fluid has a charge concentration sufficient to induce a polar fluid gate voltage that optimizes the gate voltage versus channel current characteristics of the field effect transistor in response to the target analyte.
  • the constant current source maintains a constant current through the field effect transistor.
  • the constant voltage source maintains a constant voltage over the field effect transistor.
  • a voltage output or a current output is communicated, through a wired or wireless transmission, to a digital platform.
  • the digital platform comprises a smart phone, a tablet computer, a smart watch, an in-car entertainment system, a laptop computer, desktop computers, a computer terminal, a television system, e-book reader, a wearable device, or any other type of computing device that processes digital input.
  • Figure 1 A depicts an embodiment of the prior art, illustrating a graphene field-effect transistor (gFET).
  • gFET graphene field-effect transistor
  • Figure IB depicts an embodiment of the prior art, showing current between source and drain as controlled by gate voltage.
  • Figure 2A depicts an exemplary embodiment, showing a gateless graphene field-effect (g-gFET).
  • g-gFET gateless graphene field-effect
  • Figure 2B depicts an exemplary embodiment, showing a g-gFET.
  • Figure 2C depicts an exemplary embodiment, showing a g-gFET.
  • Figure 2D depicts an exemplary embodiment, showing a g-gFET.
  • Figure 3 A depicts an exemplary embodiment, showing a polar fluid gate terminal (PFGT) where polar fluid has no motion.
  • PFGT polar fluid gate terminal
  • Figure 3B depicts an exemplary embodiment, showing a polar fluid gate terminal where polar fluid flows in a first direction.
  • Figure 3C depicts an exemplary embodiment, showing a polar fluid gate terminal where polar fluid flows in a second direction.
  • Figure 4A depicts an exemplary embodiment, showing a base device as depicted in Figures 2A-2D with dielectric and gate metal. Gate potential is measured between the gate metal and the ground.
  • Figure 4B depicts an exemplary embodiment, showing a base device as depicted in Figures 2A-2D with an added metal electrode in the PFGT. Gate potential is measured between the metal electrode and the ground.
  • Figure 4C depicts an exemplary embodiment, showing a base device as depicted in Figures 2A-2D augmented with the dielectric and gate metal, and a metal electrode in the PFGT. Two gate potentials are measured as indicated.
  • Figure 5A depicts an exemplary embodiment, showing a GFET used in conjunction with a constant current source.
  • Figure 5B depicts an exemplary embodiment, showing a GFET used in conjunction with a constant voltage source.
  • igure 6 illustrate an exemplary embodiment, showing selectivity
  • Figure 7 illustrates an exemplary embodiment, showing sensitivity measurements for NaCl response in DI water.
  • Figure 8 illustrates an exemplary embodiment, showing chloride response in sweat.
  • Figure 9 illustrates an exemplary embodiment, showing selectivity measurements of Glucose response in DI water.
  • Figure 10 illustrates an exemplary embodiment, showing glucose response in NaCl vs glucose response in DI water.
  • Figure 11 illustrates an exemplary embodiment, showing selectivity measurements of Glucose response in NaCl water.
  • Figure 12 illustrates an exemplary embodiment, showing sensitivity measurements of D-Glucose response in DI water.
  • Figure 13 illustrates an exemplary embodiment, showing functionalization steps visualized through the GFET fabrication.
  • Figure 14 illustrates an exemplary embodiment, showing D-glucose response in sweat.
  • Figure 15 illustrates an exemplary embodiment, showing D-glucose response in blood.
  • Figure 16 illustrates an exemplary embodiment, showing measurements correlation between blood glucose and sweat glucose.
  • Figure 17 illustrates an exemplary embodiment, showing selectivity measurements of lactic acid response in DI water.
  • Figure 18 illustrates an exemplary embodiment, showing selectivity measurements of lactic acid response in various solutions.
  • Figure 19 illustrates an exemplary embodiment, showing lactic acid response in NaCl vs lactic acid response in DI water.
  • Figure 20 illustrates an exemplary embodiment, showing lactic acid functionalization steps visualized through the GFET fabrication.
  • Figure 21 illustrates an exemplary embodiment, showing a model for sensor correlation with sweat sodium concentration.
  • Figure 22 illustrates an exemplary embodiment, showing a model for sensor correlation with sweat glucose concentration.
  • Figure 23 illustrates an exemplary embodiment, showing a trans-conductance curve for PFT.
  • Graphene Field Effect Transistors in General [0070] Graphene possesses a remarkable mechanical resistance; this enables thicknesses on the order of a monolayer or bilayer to be subjected to a substantial mechanical stress without losing its primary electrical properties. Such mechanical strength makes graphene an ideal candidate to replace the current generation of transparent conductive oxides (TCO), led by Indium Tin Oxide (ITO). Unlike graphene, ITO is brittle and susceptible to mechanical stress; however its low sheet resistance and high transparency are enough to offset its high material costs. The production of large area and low sheet resistance graphene sheets, on the other hand, is a relatively straightforward and scalable process using chemical vapor deposition (CVD), yielding few atomic layers with transparency higher than 90% and sheet resistances lower than 100 after proper treatment.
  • CVD chemical vapor deposition
  • Graphene FETs are generally fabricated on a Si wafer covered with a Si02 layer, and graphene forms the transistor channel.
  • the graphene transistor consists of three terminals: source and drain metal electrodes contacting the graphene channel and a global back gate enabled by the doped Si substrate.
  • Figure IB illustrates electric current between the source and drain as controlled by gate voltage.
  • the resulting curve of current flow the source and drain takes a "V" shape.
  • I D S channel current
  • FETs field effect transistors
  • Figures 2 A through 2D depicts various embodiments of FETs that do not have a physical gate.
  • Figure 2A depicts an example graphene-based FET 210, which includes a substrate 1, a source electrode 2, a drain electrode 3, receptors 4, a graphene layer 5, and back polymer 6.
  • substrate 1 can be polyamide, PET, PDMS, PMMA, other plastics, silicon dioxide, silicon, glass, aluminum oxide, sapphire, germanium, gallium arsenide, indium phosphide, an alloy of silicon and germanium, fabrics, textiles, silk, paper, cellulose based materials, insulator, metal, semiconductor, can be rigid, flexible or any combination thereof.
  • substrate 1 can be a silicon carbide substrate and graphene layer 5 can be epitaxially grown on the silicon carbide substrate directly by sublimation of silicon from the silicon carbide substrate ( Figure 2B).
  • Source electrode 2 is the electrode region in a field-effect transitor from which majority carriers flow into the interelectrode conductivity channel.
  • Exemplary material that can be used as a source electrode includes but is not limited to silver, gold, carbon, graphite ink, conductive fabrics, conductive textiles, metals, conductive materials, conductive polymers, conductive gels, ionic gels, conductive inks, non-metallic conductive materials.
  • Drain electrode 3 is the electrode on the opposite side from source electrode 2.
  • Exemplary material that can be used as a source electrode includes but is not limited to silver, gold, carbon, graphite ink, conductive fabrics, conductive textiles, metals, conductive materials, conductive polymers, conductive gels, ionic gels, conductive inks, non-metallic conductive materials .
  • graphene layer 5 can have a uniform thickness, preferably a predetermined thickness of one or more monolayers of graphene.
  • a uniform and preferably predetermined thickness provides control of the sensing properties and enables the formation of reproducible devices with low variability between individual sensors.
  • graphene layer 5 can be an epitaxial layer and the graphene layer substrate may be the substrate on which the graphene layer was epitaxially grown.
  • the graphene layer substrate may be the substrate on which the graphene layer was epitaxially grown.
  • graphene layer 5 can be surface treated with receptors 4 for selectivity so that only selected types of analytes are detected by the graphene layer.
  • Exemplary receptors 4 include but are not limited to pyrene boronic acid (PBA), N- hydroxysuccinimide ester (Pyrene- HS), organic chemicals, aromatic molecules, cyclic molecules, enzymes, proteins, antibodies, viruses, single stranded DNAs (ssDNAs), aptamers, inorganic materials, synthetic molecules, biological molecules.
  • PBA pyrene boronic acid
  • Pyrene- HS N- hydroxysuccinimide ester
  • organic chemicals aromatic molecules
  • cyclic molecules enzymes, proteins, antibodies, viruses, single stranded DNAs (ssDNAs), aptamers, inorganic materials, synthetic molecules, biological molecules.
  • graphene layer 5 and/or so that certain types of chemicals are prevented from reaching the chemically sensitive channel may comprise deposition of metal particles and/or polymers.
  • Back polymer 6 is used to provide mechanical support to the graphene. And when doped, can add a new modality to the sensing response.
  • the back polymer can be doped with biomolecules that could also bind to specific targets and contribute to the resistance change of the transistor channel.
  • Devices 220, 230 and 240 are variations of device 210.
  • back polymer layer 6 is omitted.
  • receptor layer 4 is omitted.
  • both back polymer layer 6 and receptor layer 4 are omitted.
  • a device or a base device can be any of devices 210, 220, 230, and 240.
  • Graphene is an allotrope of carbon in the form of a two-dimensional, atomic- scale, hexagonal lattice in which one atom forms each vertex. It is the basic structural element of other allotropes, including graphite, charcoal, carbon nanotubes and fullerenes. It can be considered as an indefinitely large aromatic molecule, the ultimate case of the family of flat polycyclic aromatic hydrocarbons.
  • graphene is a monolayer of carbon atoms. Each carbon atom in graphene has four electrons. Through three of these electrons the carbon atom binds to three nearest neighboring carbon atoms to form a hexagonal lattice. For each atom, a forth electron is delocalized on the whole graphene layer, which allows the conduction of an electron current.
  • FIG. 3 A depicts an exemplary embodiment, showing a polar fluid gate terminal, where the polar fluid has no motion. As depicted, charges of the polar or ionic components are redistribution in the polar fluid to create a polar fluid gate terminal (PFGT) and an induced fluid gate voltage (V F G)- This voltage can result in a shift in the x-axis (voltage) in the V-shaped current vs. fluid gate voltage curve.
  • PFGT polar fluid gate terminal
  • V F G induced fluid gate voltage
  • a shift towards the tip of the V-shaped curve can lead better sensitivity.
  • Such a shift can be caused by a polar liquid induced gate voltage.
  • the polar liquid induced gate voltage is associated with the concentration of charged particles within the polar fluid.
  • the concentration can reflect the total quantity of all negatively charged particles or all positively charged particles.
  • the shift in the V-shaped curve can correlate with a wide range of charged particle concentrations.
  • a shift is correlated with a charged particle concentration as low as 1 femto g/L (e.g., NaCl).
  • a shift is correlated with a charged particle concentration as high as 300 g/L (e.g., NaCl).
  • FIG. 3B depicts an exemplary embodiment, showing a polar fluid gate terminal, where the polar fluid flows in a first direction.
  • the magnitude of the gate potential (V F G) will be directly proportional to the flow rate of the polar fluid.
  • the sign or direction of V F G will depend on the direction of flow of the polar fluid; e.g., along the source drain terminal and across the source drain terminal. For example, if the gate voltage is positive along the source drain direction, it will be negative in the reverse direction, and vice versa.
  • the polar fluid is flowing across the source drain voltage, if the gate voltage is positive along the Y direction, it will be negative in the -Y direction and vice versa.
  • the direction of the polar fluid flow changes, the direction of the gate voltage would also change.
  • Figure 3C depicts an exemplary embodiment, showing a polar fluid gate terminal, where the polar fluid flows in a second direction opposite to the first direction. Detecting Gate Voltage at Polar fluid gate terminal
  • Figures 4A through 4C illustrate set up by which gate voltage at a polar fluid gate terminal (PFGT) is determined.
  • PFGT polar fluid gate terminal
  • Figure 4A depicts an exemplary embodiment, showing a base device with a dielectric layer 7 and a gate metal 8.
  • the base device can be any of the devices depicted in Figures 2A-2D such as 210, 220, 230 and 240.
  • Gate potential is measured between the gate metal and the ground.
  • Dielectric layer 7 is added underneath the substrate of the base device (e.g., substrate 1 as depicted in Figures 2A through 2D).
  • Gate metal 8 is added underneath dielectric layer 7.
  • Gate metal 8 is added only to measure the induced gate voltage, no voltage will be applied through gate metal 8.
  • Vgl can vary in non-linear way depending on the PFGT device characteristics and type of channel. For example, if the channel is graphene (ambipolar), Vgl can follow the transconductance response typical to a graphene device.
  • Figure 4B depicts an exemplary embodiment, showing a base device as depicted in Figures 2A-2D with an added metal electrode in the PFGT. Gate potential is measured between the metal electrode and the ground.
  • Vg2 is the top gate voltage formed by the double layer capacitance between added metal electrode and active channel. Vg2 can vary in non-linear way depending on the PFGT device characteristics and type of channel. For example if the channel is graphene (ambipolar), thenVg2 will follow the transconductance response typical to a graphene device (see, e.g., Figure 23).
  • Figure 4C depicts an exemplary embodiment, showing a base device as depicted in Figures 2A-2D augmented with the dielectric and gate metal, and a metal electrode in the PFGT.
  • Two gate potentials are measured as indicated.
  • the two gate potentials (Vgl and Vg2) are electrical outputs that are modulated using the source drain current/voltage and the induced PFG.
  • the simultaneous measurements of Vgl and Vg2 creates a tri -gated structure that can used develop next generation microprocessors, logic gates, computational circuits, radio frequency (RF) devices, sensors, and etc.
  • RF radio frequency
  • Figure 4C depicts an exemplary embodiment, showing a base device as depicted in Figures 2A-2D augmented with the dielectric and gate metal, and a metal electrode in the PFGT.
  • Two gate voltages e.g., Vgl and Vg2 are supplied to the PFGT to modulate the overall electrical characteristics of the PFGT device for a desired application.
  • the simultaneous modulation by Vgl and Vg2 creates a tri-gated structure that can used to shift the device operation to a desired electrical performance in a more controlled fashion using minimal energy.
  • Such a device can be utilized to develop next generation microprocessors, logic gates, computational circuits, radio frequency (RF) devices, sensors, and etc.
  • RF radio frequency
  • Figure 5 A depicts an exemplary embodiment, showing a circuit used for sensor readout via a polar fluid graphene field effect transistor (PFGFET).
  • PFGFET polar fluid graphene field effect transistor
  • Ic constant current
  • VOU T Output voltages
  • R current limiting resistor
  • FIG. 5B depicts an exemplary embodiment, showing another circuit used for sensor readout via PFGFET.
  • a constant voltage (Vs) is supplied to the PFGFET.
  • Currents or chargers ( ⁇ ) are read from the PFGFET using a current limiting resistor (R). The electrical current output is then calibrated to the concentrations of the analyte being sensed.
  • a polymer was disposed on graphene with thickness normally less than 0.5 mm, which was then separated from the catalytic substrate where the graphene was grown.
  • a flexible polymer platform for the sensing system was used for staging the graphene polymer composite and two metal electrical contacts.
  • the graphene polymer composite was bound to the flexible polymer platform.
  • a solution of desired linker molecule is deposited on the graphene polymer composite to incubate. The excess linker molecule solution was removed from the graphene polymer composite; and the two metal electrical contacts were deposited on both edges of the graphene polymer composite.
  • the graphene polymer complex was then placed on a polymer substrate, such as teflon, polyimide, and etc., and then heated for 1-10 mins at 80-150 degree Celsius to remove any impurities.
  • a polymer substrate such as teflon, polyimide, and etc.
  • the GFET sensor was then ready for use. In some cases, receptors for specific analytes were deposited on the graphene layer.
  • a sensor system for analyte sensing through sweat where the sensor comprised of:
  • o a graphene polymer composite bound to the flexible polymer platform; o asource electrode and a drain electrode located in a sensor configuration on
  • each of the source and drain electrodes comprised of conductive metals; o graphene polymer composite layer was functionalized with a linker molecule for the desired analyte biosensing, between the two electrodes; and
  • a method of determining analyte concentration through sweat comprised the following steps:
  • analyte binds to the linker molecule by releasing an electron through the linker into the channel resulting in change in potential across the channel;
  • Figure 6 shows that the GFET gave no significant response to just DI water and a linear response to increasing NaCl concentrations in DI water. The increasing
  • concentrations changed the voltage across the channel, thereby showing high selectivity towards NaCl in DI water as control.
  • Sensitivity Response of various NaCl concentrations in DI water were also measured on the GFET to study the sensitivity range of the sensor towards NaCl. Solutions with exponentially increasing concentrations of NaCl, ranging from 0. lng/dl to 10 mg/dL in DI water, were prepared. The test started with introducing 2ul of the lowest concentrations on the GFET followed by the next higher concentration after 3 minutes and so on. Here, concentrations increased logarithmically, for example, going from O. lng/dl to lng/dl, then lOng/dl, then
  • Figure 7 shows that the GFET gave no significant response to just DI water and an exponential response starting from the lowest to the highest concentration of NaCl in DI water. The increasing concentrations changed the voltage across the channel, thereby showing high sensitivity around 250 femto gram/litre towards NaCl in DI water as control.
  • Chloride Response in Sweat Measurement of chloride concentrations in human sweat was done with human subjects. The test required the subject to perform physical activity, such as running, and taking water for hydrating from time to time.
  • Figure 8 shows the real-time concentrations of sweat osmolality of two human subjects using a PFGFET attached to the skin.
  • the osmolality concentrations in sweat directly correlated to the physical performance of the individuals.
  • Subject 1 was a sprinter and subject 2 was a jogger.
  • the sprinter (subject 1) ran the same distance in a quicker pace (run 1) as compared to the jogger (subject 2 and run 2). It was observed that more intense a subject's physical activity, higher the measured body osmolality concentrations. Peaks in body osmolality were observed during periods of most intense physical activity. It was also observed that the body osmolality reduced during periods of the intense physical activity.
  • High sensitivity The GFETs functionalized with PBA exhibited a high sensitivity for NaCl with a limit of detection (LOD) of 250 femto gram/litre.
  • LOD limit of detection
  • the GFET sensors have a high signal to noise ratio, are highly selective and due to the high surface area for bonding there is higher bonding between the surface and the molecules. All these factors play a huge differentiating role, making GFETs highly sensitive.
  • Graphene FETs were functionalized with linker molecule (lock) that specifically binds to the glucose molecule in fluids.
  • linker molecule lock
  • the GFET was functionalized with Pyrene Boronic Acid (PBA). Pyrene Boronic Acid bonds to the Graphene surface using pi-pi bond. PBA forms a reversible boron-anion complex with D- glucose. Fabrications steps are the following:
  • a polymer was disposed on graphene with thickness normally less than 0.5mm, which is then separated from the catalytic substrate it was grown on.
  • the graphene polymer complex was then placed on a polymer substrate, such as teflon, polyimide, etc. and heated for 1-10 mins at 80-150 degree Celsius to remove any impurities,
  • Figure 9 shows that the GFET gave no significant response to just DI water or to lactose solutions and an exponential response to increasing D-Glucose concentrations in DI water. The increasing concentrations changed the voltage across the channel, thereby showing high selectivity towards D-Glucose with DI water as control.
  • Glucose Response in NaCl vs Glucose Response in DI water Response of various D-Glucose concentrations in DI water and NaCl solutions were measured on the GFET to study the sensitivity of the functionalized sensor towards D-Glucose in DI water vs D-Glucose in NaCl and to understand the effect of NaCl solutions.
  • Figure 10 shows that the D-Glucose response in NaCl is more amplified than D-Glucose response in DI water.
  • the polar solution providing the PFGT on the GFET amplified the electrical response across the channel thereby increasing sensitivity and providing reversibility.
  • Figure 11 shows that the GFET gave no significant response to just NaCl solutions and a linear response to solutions of increasing D-Glucose concentrations in fixed NaCl concentration versus solutions of increasing NaCl concentrations. The increasing concentrations changed the voltage across the channel, thereby showing high selectivity towards D-Glucose.
  • the GFETs (NFETs) functionalized with PBA gave a highly selective response (>95%) to glucose concentrations.
  • Figure 11 gives an idea that the functionalized glucose sensor isn't sensitive to NaCl (as the orange curve is fairly flat), whereas the glucose curve is increasing with increasing cone of glucose present in NaCl solution.
  • concentrations on the GFET followed by the next higher concentration after 3 minutes and so on.
  • concentrations increased logarithmically; e.g., from 0.25pg/l, then 2.5pg/l and so on. This was continued until all the concentrations were introduced onto the GFET.
  • Figure 12 shows that the GFET gave no significant response to just DI water and a linear response starting from the lowest to the highest concentration, with increasing concentrations the current across the channel changed, thereby showing high sensitivity around 250 femto gram/litre (i.e., 1.38e "12 mmol/1) towards D-glucose.
  • FIG. 13 Shown in Figure 13 are the current response for graphene sensor, before functionalization, after functionalization and after glucose is introduced on the sensor. This helps in understanding each stage of the GFET fabrication step and how after each stage the current response of the GFET changes. For example, it was shown in Figure 13 that the current response increases after functionalization (orange) as compared to the before functionalization (blue) this happens because linker molecules are bound by pi-pi bond and the overall charge on the surface of the graphene increases. The linker molecule attracts the glucose molecules and binds to it by using these charge clouds thereby reducing the current on the GFET as compared to its previous state.
  • D-glucose Response in Sweat and Blood Measurement of glucose concentrations in human sweat was done with human subjects. The test required the subject to perform physical activity, such as running, and taking blood samples to measure blood glucose using a blood glucose meter every few minutes. The GFETs are worn on the fore arm and lower back (eccrine sweat glands) by human subjects. Electrical responses due to the D-Glucose concentrations in sweat were transmitted and recorded continuously (every 500 milliseconds) while the subjects were performing intense physical activity (like running).
  • the physical activity was eating food.
  • his glucose will start going up as can be seen in both sweat and blood glucose.
  • the glucose level will start to come down and stabilize.
  • Figure 14 shows_the change in D-Glucose concentration in sweat, as represented by the fractional change in the voltage.
  • the blood glucose data in Figure 15 was also plotted against time for the entire duration of the workout.
  • the sweat glucose measurements were correlated with blood glucose measurements.
  • the sweat glucose values for the corresponding blood glucose values were plotted against blood (blood vs sweat) to get a correlation R 2 , which provided an idea about how well sweat glucose matched with blood glucose.
  • Figure 16 further shows measurements correlation between blood glucose and sweat glucose.
  • 3 different sensors were used for the same person for the same time.
  • Over 150 curves of sweat glucose were collected from 10 human subjects along with their blood glucose for the entire duration of the study, for correlation. The subjects performed physical activities (workouts, running, etc.) or no physical activity (sitting on a desk, etc.).
  • the GFETs functionalized with PBA exhibited a high sensitivity for D-Glucose with a limit of detection (LOD) of 250 femto gram/litre, i.e., 1.38e "12 mmol/1.
  • the existing glucose meters have an LOD between 0.3-1. lmmol/1.
  • the GFET functionalized with PBA is approx. 1010 times more sensitive than the existing standard glucose measurement devices.
  • the GFET sensors have a high signal to noise ratio, are highly selective and due to the high surface area for bonding there is higher bonding between the surface and the receptor molecules. All these factors play a huge differentiating role in making GFETs highly sensitive.
  • Graphene FETs were functionalized with linker molecule (lock) that specifically binds to the lactic acid molecules in fluids.
  • linker molecule lock
  • the GFET was functionalized with Lactate Oxidase( LOx) to the Graphene surface using an intermediate pyrene- HS linking chemistry
  • a polymer is disposed on graphene with thickness normally less than 0.5mm, which is then separated from the catalytic substrate it was grown on.
  • the graphene polymer complex is then placed on a polymer substrate, such as teflon, polyimide, etc. and heated for 1-10 mins at 80-150 degree celcius to remove any impurities,
  • the senor is ready for use.
  • Figure 17 shows that the GFET gave no significant response to just DI water and a polynomial response to increasing lactic acid concentrations in DI water, the increasing concentrations changed the voltage across the channel, thereby showing high selectivity towards lactic acid in DI water, using DI water as the control.
  • Selectivity Measurements of Lactic Acid Response in Various Solutions Response of various lactic acid concentrations in various solutions were measured on the GFET to study the sensitivity of the functionalized sensor towards lactic acid and response on a non- functionalized sensor. Solutions with varying concentrations of lactic acid ranging for 0-25mM in NaCl and NaCl-Glucose were prepared. The test started with introducing 2ul of the lowest concentrations on the GFET followed by the next highest concentration after 3 minutes and so on. This was continued until all the concentrations were introduced onto the GFET, separately for each solution.
  • Figure 18 shows that the GFET gave no significant response to just NaCl or NaCl-Glucose control and a polynomial response to increasing lactic acid concentrations in NaCl and NaCl-Glucose solution. The increasing concentrations changed the voltage across the channel, thereby showing high selectivity towards lactic acid. There was no significant response on the non-functionalized sensor for the lactic acid NaCl solution, further emphasizing on the selectivity and sensitivity of the sensor towards lactic acid.
  • Lactic Acid Response in NaCl vs. Lactic Acid Response in DI Water:
  • Figure 19 shows that the lactic acid response in NaCl is less amplified than lactic acid response in DI water.
  • Figure 20 The current responses for graphene sensor, before functionalization, after functionalization and after lactic acid is introduced on the sensor are depicted in Figure 20. This helps in understanding each stage of the GFET fabrication step and how after each stage the current response of the GFET changes. For example, Figure 20 shows that the current response decreases after functionalization (orange) as compared to before functionalization (blue). The linker molecule attracts the lactic acid molecules and binds to it thereby reducing the current on the GFET as compared to its previous state.
  • the GFETs functionalized with Pyrene NHS exhibited a high sensitivity for lactic acid with a limit of detection (LOD) of 250 femto gram/litre; i.e., 2.78e- 12 mmol/1.
  • the existing lactic acid meters have an LOD between 0.001-10 mmol/1.
  • the GFET functionalized with Pyrene NHS is approx. 108 times sensitive than the existing standard lactic acid measurement devices.
  • the GFET sensors have a high signal to noise ratio, are highly selective and due to the high surface area for bonding there is higher bonding between the surface and the receptor molecules. All these factors play a huge differentiating role in making GFETs highly sensitive.
  • Sweat Salt Concentration Correlation Figure 21 represents, the sweat sensor response for a corresponding sweat sodium concentration.
  • Increasing concentrations of NaCl 0.1 mg/dl to 100 mg/dl were added on the graphene sensor, every 3 minutes. The test started with dropping 2 ul of the lowest concentration (e.g., 0.1 mg/dl) followed by the next higher concentration (e.g., 0.2 mg/dl) and so on with an interval of 3 minutes.
  • Corresponding fractional change in voltage was measured. This was repeated for 10 different sensors and a max error of 15% was observed. This acts as a model for correlation between sweat sodium and corresponding change in voltage.
  • NaCl solution with increasing concentrations ranging from 0.1 ng/dl to 1 mg/dl is dropped every 3 minutes on the sensor.
  • the test starts with dropping 2 ul of the lowest concentration (e.g., 0.1 ng/dl) followed by the next higher concentration (1 ng/dl) and so on with an interval of 3 minutes.
  • both the debye length and the gating effect are a function of the concentration of the polar molecules.
  • DI is more dominant, due to which more holes are created and we see a drop in the voltage.
  • the concentration of the NaCl increasing in the solution it becomes more dominant and more electrons are created near the debye layer, thereby showing an increase in the voltage.
  • the numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are

Abstract

L'invention concerne des transistors à effet de champ à échelle nanométrique (NFET), par exemple des transistors à effet de champ à base de graphène (GFET), qui ne comportent par de grilles physiques. Au lieu de cela, la grille de ces transistors est constituée par un fluide polaire. La présente invention concerne également des systèmes et des procédés d'utilisation desdits transistors.
EP17812823.7A 2016-06-30 2017-06-30 Dispositifs à effet de champ dont la grille est constituée par un fluide polaire Pending EP3472607A4 (fr)

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EP3819260A1 (fr) * 2019-11-07 2021-05-12 Infineon Technologies AG Matériau composite, capteur de gaz chimiorésistant, système de capteur de gaz chimiorésistant et son procédé de fabrication et d'utilisation
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