WO2020152453A1 - Transistor organique en couches minces doté d'un groupe protique sur des électrodes de source et de drain pour déterminer la présence et/ou la concentration d'ester - Google Patents

Transistor organique en couches minces doté d'un groupe protique sur des électrodes de source et de drain pour déterminer la présence et/ou la concentration d'ester Download PDF

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WO2020152453A1
WO2020152453A1 PCT/GB2020/050126 GB2020050126W WO2020152453A1 WO 2020152453 A1 WO2020152453 A1 WO 2020152453A1 GB 2020050126 W GB2020050126 W GB 2020050126W WO 2020152453 A1 WO2020152453 A1 WO 2020152453A1
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gas sensor
otft
source
drain electrodes
ester
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PCT/GB2020/050126
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English (en)
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Pascal CACHELIN
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Sumitomo Chemical Co., Ltd
Cambridge Display Technology Limited
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Publication of WO2020152453A1 publication Critical patent/WO2020152453A1/fr

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    • 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
    • G01N27/4141—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for gases
    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • 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
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0047—Organic compounds
    • 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
    • G01N33/02—Food
    • G01N33/025—Fruits or vegetables

Definitions

  • Embodiments of the present disclosure relate to organic thin film transistor gas sensors. More particularly, but not by way of limitation, some embodiments of the present disclosure relate to organic thin film gas sensors configured to detect esters.
  • Thin film transistors have been previously used as gas sensors.
  • TFTs Thin film transistors
  • such use of thin film transistors as gas sensors is described in Feng et al, Unencapsulated Air- stable Organic Field Effect Transistor by All Solution Processes for Low Power Vapor Sensing, SCIENTIFIC REPORTS 6:20671 DOI: 10.1038/srep20671 and Besar et al, Printable ammonia sensor based on organic field effect transistor, ORGANIC ELECTRONICS, Vol. 15, Issue 11, Pages 3221-3230 (November 2014).
  • a semiconducting layer is in electrical contact with source and drain electrodes and a gate dielectric is disposed between the semiconducting layer and a gate electrode.
  • U.S. Patent No. 8,686,404 discloses an electronic circuit containing first and second organic thin film transistors in which each organic thin film transistor includes bottom source/drain electrodes having a self-assembled monolayer formed thereon.
  • Volatile organic compounds may be released during decay of food, for example as described in Phan, NT., Kim, KH., Jeon, EC. et al. ENVIRON MONIT ASSESS (2012) 184: 1683. https://doi.org/10.1007/sl0661-011-2070-2, Analysis of volatile organic compounds released during food decaying processes. J Dixon and E Hewett, NEW ZEALAND JOURNAL OF CROP AND HORTICULTURAL SCIENCE, Vol. 28: 155-173, Factors affecting apple aroma/flavour volatile concentration: a review (2000) discloses that apple flavour develops during ripening and maximum endogenous volatile concentration occurs at the climacteric peak. M. Espino-Diaz el al, FOOD TECHNOL BIOTECHNOL.; 54(4): 375-397, Biochemistry of Apple Aroma: A Review (2016 Dec.) discloses flavour of apples defined by volatile aroma compounds.
  • SUMMARY Ester compounds can be present in various gaseous environments.
  • butyl acetate is produced by certain fruits, for example apples.
  • OFTs organic thin film transistors
  • concentration of volatile ester compounds produced by fruit may be useful in determining ripeness of the fruit.
  • sensitivity of an OTFT gas sensor to ester compounds may be increased by treatment of the source and drain electrodes of the OTFT gas sensor with certain compounds.
  • a method of identifying the presence and / or concentration of an ester in a gaseous environment including measurement of a response of an organic thin film transistor gas sensor to the environment and determining from the measured response the presence and / or concentration of the ester.
  • the OTFT gas sensor may have source and drain electrodes in electrical contact with an organic semiconductor layer; a gate electrode; and a gate dielectric between the organic semiconductor layer and the gate electrode.
  • a protic group may be bound to a surface of the source and drain electrodes.
  • the OTFT gas sensor may be configured to provide for gas communication of the ester in the environment with the protic group.
  • Figure 1 illustrates a bottom gate, bottom contact OTFT gas sensor according to some embodiments
  • Figure 2 illustrates a bottom gate, top contact OTFT gas sensor according to some embodiments
  • Figure 3 illustrates a top gate, bottom contact OTFT gas sensor according to some embodiments
  • Figure 4 illustrates a top gate, top contact OTFT gas sensor according to some embodiments.
  • Figure 5 is a graph of drain current vs. time upon exposure of two OTFT gas sensors according to some embodiments and a comparative OTFT gas sensor to methyl hexanoate.
  • the words “comprise,” “comprising,” and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to.”
  • the terms “connected,” “coupled,” or any variant thereof means any connection or coupling, either direct or indirect, between two or more elements; the coupling or connection between the elements can be physical, logical, electromagnetic, or a combination thereof.
  • the words “herein,” “above,” “below,” and words of similar import when used in this application, refer to this application as a whole and not to any particular portions of this application.
  • words in the Detailed Description using the singular or plural number may also include the plural or singular number respectively.
  • the word "or,” in reference to a list of two or more items, covers all of the following interpretations of the word: any of the items in the list, all of the items in the list, and any combination of the items in the list.
  • a material“over” a layer is meant that the material is in direct contact with the layer or is spaced apart therefrom by one or more intervening layers.
  • a material“on” a layer is meant that the material is in direct contact with that layer.
  • a layer“between” two other layers as described herein may be in direct contact with each of the two layers it is between or may be spaced apart from one or both of the two other layers by one or more intervening layers.
  • inventions introduced here can be embodied as special-purpose hardware (e.g., circuitry), as programmable circuitry appropriately programmed with software and/or firmware, or as a combination of special-purpose and programmable circuitry.
  • embodiments may include a machine -readable medium having stored thereon instructions which may be used to program a computer (or other electronic devices) to perform a process.
  • the machine-readable medium may include, but is not limited to, floppy diskettes, optical disks, compact disc read-only memories (CD-ROMs), magneto-optical disks, ROMs, random access memories (RAMs), erasable programmable read-only memories (EPROMs), electrically erasable programmable read-only memories (EEPROMs), magnetic or optical cards, flash memory, or other type of media / machine-readable medium suitable for storing electronic instructions.
  • the machine-readable medium includes non-transitory medium, where non-transitory excludes propagation signals.
  • a processor can be connected to a non-transitory computer-readable medium that stores instructions for executing instructions by the processor.
  • FIG. 1 is a schematic illustration of a bottom contact, bottom gate OTFT gas sensor according to some embodiments.
  • the bottom contact bottom gate OTFT comprises a gate electrode 103 disposed over a substrate 101, e.g. a glass or plastic substrate; source and drain electrodes 107, 109; a dielectric layer 105 between the gate electrode and the source and drain electrodes; and an organic semiconductor layer 111 in electrical contact with the source and drain electrodes.
  • a protic layer 113 comprising a protic group is bound to a surface of the source and drain electrodes and is disposed between the source and drain electrodes and the organic semiconducting layer. The protic layer may be in direct contact with the organic semiconducting layer.
  • FIG 2 is a schematic illustration of a top-contact bottom gate OTFT gas sensor according to some embodiments.
  • the top-contact bottom gate OTFT is as described with reference to Figure 1 except that the organic semiconductor layer 111 is between the dielectric layer 105 and the source and drain electrodes 107, 109.
  • FIG. 3 is a schematic illustration of a top gate bottom contact OTFT gas sensor according to some embodiments.
  • the top gate bottom contact OTFT gas sensor comprises source and drain electrodes 107, 109 disposed over a substrate; an organic semiconductor layer 111 in electrical contact with the source and drain electrodes; a dielectric layer 105 between the gate electrode 103 and the organic semiconductor layer; and protic layer 113 comprising a protic group is bound to a surface of the source and drain electrodes and between the source and drain electrodes and the organic semiconducting layer.
  • the organic semiconducting layer is disposed between the source and drain electrodes and the dielectric layer.
  • FIG 4 is a schematic illustration of a top gate top contact OTFT gas sensor according to some embodiments.
  • the top gate OTFT gas sensor is as described with reference to Figure 3 except that the organic semiconducting layer is disposed between the substrate and the source and drain electrodes.
  • the dielectric layer of a top-gate OTFT gas sensor as described herein, e.g. as described with reference to Figures 3 and 4, is a gas-permeable material, preferably an organic material.
  • the top gate electrode of a top gate OTFT gas sensor as described herein, e.g. as described with reference to Figures 3 and 4 is patterned, e.g., comprises fingers, comb like structures and/or the like, to provide channels, openings and/or the like that allow passage of gas through the top gate electrode to the protic layer.
  • the OTFT gas sensor comprises a second semiconducting layer adjacent to the organic semiconducting layer.
  • Such an OTFT gas sensor may be as described in any one of Figures 1-4, the OTFT gas sensor further comprising the second semiconducting layer adjacent to the organic semiconducting layer.
  • the second semiconducting layer is disposed between the source and drain electrodes and the organic semiconducting layer.
  • the organic semiconducting layer is disposed between the source and drain electrodes and the second semiconducting layer.
  • the OTFT gas sensor may be exposed to a gaseous environment and a response of the OTFT gas sensor may be measured. The response may be a change in drain current.
  • a measurement unit configured to measure the response of the OTFT gas sensor may be in wired or wireless communication with processor unit configured to determine a presence, a concentration, and / or a change in concentration, of an ester in the environment.
  • the response of the OTFT gas sensor to an environment may be a change which is directly proportional to a concentration of ester in the environment, or directly proportional to a derivative of the concentration of ester in the environment.
  • the OTFT gas sensor may be calibrated by measuring response of the OTFT gas sensor to one or more known concentrations of ester in an environment.
  • the OTFT gas sensor may be part of a gas sensor system in which the OTFT gas sensor is a first gas sensor and in which the gas sensor system comprises one or more further OTFT gas sensors different from the first OTFT gas sensor.
  • The, or each, further OTFT gas sensor may be configured to detect a second gas in the environment other than an ester.
  • the first OTFT gas sensor configured to detect an ester has greater sensitivity to the ester than to a second gas.
  • the gas sensor system comprises a second OTFT gas sensor configured to detect a second gas, the second OTFT gas sensor having greater sensitivity to the second gas than the first gas.
  • the second gas may be an alkene, optionally an alkene comprising a conjugated alkene group, for example styrene or famesene.
  • the alkene may be capable of binding to source and drain electrodes of the second OTFT gas sensor. Such binding to source and drain electrodes of the first OTFT gas sensor may be inhibited by the pro tic group.
  • sensitivity of an OTFT gas sensor to a gas is meant a maximum percentage change in drain current upon exposure of the OTFT gas sensor to a given concentration of the gas.
  • first and second OTFT gas sensors may have one or more of the following differences:
  • the second OTFT gas sensor may comprise one or more OTFT gas sensors as described with reference to Figures 1-4 in which the protic layer is not present, e.g. in which the organic semiconducting layer is in direct contact with the source and drain electrodes or a non-protic layer is disposed on a surface of the source and drain electrodes and between the organic semiconducting layer and the surface of the source and drain electrodes.
  • Different gate arrangements of the first and second OTFT gas sensors e.g. top gate for one of the first and second OTFT gas sensors and bottom gate for the other OTFT gas sensor.
  • Different OTFT device types e.g. top gate for one of the first and second OTFT gas sensors and bottom gate for the other OTFT gas sensor.
  • Different organic semiconductors for the first and second OTFT gas sensors e.g. a crystalline organic semiconductor for one of the first and second OTFT gas sensors and amorphous for the other OTFT gas sensor.
  • Different numbers of semiconducting layers e.g. an organic semiconducting layer as the only semiconducting layer for one of the first and second OTFT gas sensors and at least one further semiconducting layer for the other OTFT gas sensor.
  • the gas sensor system may comprise one or more control OTFT gas sensors to provide a baseline for measurements of the first and second OTFT gas sensors to take into account variables such as one or more of humidity, temperature, pressure, variation of sensor parameter measurements over time (such as variation of OTFT sensor drain current over time), and gases other than a target gas or target gases in the atmosphere.
  • One or more control OTFT gas sensors may be isolated from the atmosphere, for example by encapsulation of the or each OFT control sensor, to provide a baseline measurement other than gases in the atmosphere.
  • Each of the OTFT gas sensors of the gas sensor system may be supported on a common substrate and / or contained in a common housing.
  • each OTFT gas sensor of the gas sensor system may be connected to a common power source, or two or more of the OTFT gas sensors may be powered by different power sources.
  • power to all of the OTFT gas sensors of the gas sensor system may be controlled by a single switch or power to two or more of the OTFT gas sensors may be controlled by different switches.
  • the protic layer is a monolayer.
  • the protic group is formed from a compound capable of binding to the source and drain electrodes, optionally a compound of formula (I):
  • R 1 is an organic residue
  • X 1 is a binding group for binding to the surface of the source and drain electrodes
  • Y is a protic group
  • R 1 is a C 1-30 hydrocarbon group which may be unsubstituted or substituted with one or more substituents.
  • Exemplary C 1-30 hydrocarbon groups are: linear, branched or cyclic C 6-30 alkylene; C 6-20 arylene groups, preferably phenylene; and phenylene-C 1-20 alkylene.
  • a preferred substituent of the C 1-30 hydrocarbon group is fluorine, and one or more H atoms of the C 1-30 hydrocarbon group may be replaced with fluorine.
  • Y is -NH 2 .
  • X 1 is SH.
  • R 1 is a hydrocarbon residue, e.g. C 6-20 aromatic groups, preferably phenyl, phenyl with one or more C 1-20 alkyl groups; and phenyl-C 1-20 alkyl which may be substituted with one or more C 1-20 alkyl groups.
  • An exemplary compound of formula (I) is 4-aminobenzenethiol:
  • the protic layer consists of one or more protic groups.
  • the protic layer further comprises one or more non-protic groups.
  • the non-protic group is formed from a compound of formula (II): X 2 -R 2
  • X may be selected from groups described with reference to X .
  • R may be, without limitation, a C 1-30 hydrocarbyl group which may be unsubstituted or substituted with one or more substituents.
  • Exemplary C 1-30 hydrocarbyl groups are: linear, branched or cyclic C 6-30 alkyl; C 6-20 aryl, preferably phenyl; and C 1-20 alkylene-phenylene.
  • a preferred substituent of the C 1-30 hydrocarbyl group if present, is fluorine, and one or more H atoms of the C 1-30 hydrocarbyl group may be replaced with fluorine.
  • Exemplary compounds of formula (II) are:
  • the protic group and / or, if present, the non-protic group may be selected according to the effect, if any, it has on the work function of the source and drain electrodes and the required charge injection requirements of the OTFT gas sensor such as the work function - organic semiconductor highest occupied molecular orbital (HOMO) gap in the case of a p-type OTFT gas sensor or the work function - organic semiconductor lowest unoccupied molecular orbital (LUMO) gap in the case of a n-type OTFT gas sensor.
  • HOMO work function - organic semiconductor highest occupied molecular orbital
  • LUMO work function - organic semiconductor lowest unoccupied molecular orbital
  • a monolayer comprising the protic group and, if present, the non-protic group may be formed on the source and drain electrodes by depositing thereon a binding compound for forming the protic group and, optionally, a binding compound for forming the non-protic group, for example from a solution of the binding compound or compounds in one or more solvents.
  • the binding compound or compounds may be selectively deposited onto the source and drain electrodes only, or may be deposited by a non-selective process such as spin-coating or dip-coating.
  • a bottom-contact OTFT gas sensor (top gate or bottom gate) may be formed by depositing a binding compound or binding compounds onto the source and drain electrodes over a dielectric layer and then depositing the organic semiconducting layer. Binding compound which is not bound to the source and drain electrodes, for example binding compound on the dielectric layer or the substrate following a non-selective deposition process, may be removed by washing.
  • Organic semiconducting layer
  • Organic semiconductors as described herein may be selected from conjugated non polymeric semiconductors; polymers comprising conjugated groups in a main chain or in a side group thereof; and carbon semiconductors such as graphene and carbon nanotubes.
  • An organic semiconductor layer of an OTFT gas sensor as described herein may comprise or consist of a semiconducting polymer and / or a non-polymeric organic semiconductor.
  • the organic semiconductor layer may comprise a blend of a non-polymeric organic semiconductor and a polymer.
  • Exemplary organic semiconductors are disclosed in WO 2016/001095, the contents of which are incorporated herein by reference.
  • the organic semiconductor may be crystalline or amorphous.
  • the organic semiconducting layer may be deposited by any suitable technique, including evaporation and deposition from a solution comprising or consisting of one or more organic semiconducting materials and at least one solvent.
  • exemplary solvents include benzenes with one or more alkyl substituents, preferably one or more C 1-10 alkyl substituents, such as toluene and xylene; tetralin; and chloroform.
  • Solution deposition techniques include coating and printing methods, for example spin coating dip-coating, slot-die coating, ink jet printing, gravure printing, flexographic printing and screen printing.
  • the organic semiconducting layer has a thickness in the range of about 10-200 nm.
  • the second semiconducting layer if present, comprises or consists of a transition metal halide or a pseudohalide.
  • the transition metal halide or pseudohalide may be a metal complex, optionally a coordination polymer.
  • the transition metal of the transition metal halide or pseudohalide is optionally copper (I), silver (I) or cobalt and is preferably Cu (I).
  • the halide of a semiconducting transition metal halide is selected from fluoride, chloride, bromide, iodide or astatide.
  • the pseudohalide of a semiconducting transition metal pseudohalide is selected from thiocyanate, selenocyanate and tellurocyanate.
  • the transition metal halide or pseudohalide is selected from copper thiocyanate (CuSCN); silver thiocyanate (AgSCN); cuprous iodide (Cul). copper selenocyanate (CuSeCN) and copper tellurocyanate (CuTeCN). Copper thiocyanate is particularly preferred.
  • the source and drain electrodes can be selected from a wide range of conducting materials for example a metal (e.g. gold), metal alloy, metal compound (e.g. indium tin oxide) or conductive polymer.
  • a metal e.g. gold
  • metal alloy e.g. gold
  • metal compound e.g. indium tin oxide
  • conductive polymer e.g. gold
  • the source and drain electrode material may be selected according to its ability to bind to the protic group.
  • the source and drain electrodes are preferably gold.
  • the gate electrode may be selected from any conducting material, for example a metal (e.g. aluminium), a metal alloy, a conductive metal compound (e.g. a conductive metal oxide such as indium tin oxide) or a conductive polymer.
  • a metal e.g. aluminium
  • a metal alloy e.g. aluminum
  • a conductive metal compound e.g. a conductive metal oxide such as indium tin oxide
  • a conductive polymer e.g. a conductive metal oxide such as indium tin oxide
  • the length of the channel defined between the source and drain electrodes of the source and drain and gate electrodes of an OTFT gas sensor as described herein may be up to 500 microns, preferably less than 200 microns, more preferably less than 100 microns.
  • the dielectric layer may comprise one or more organic materials, one or more inorganic materials or a mixture thereof.
  • dielectric materials are selected from those disclosed in Chem. Rev., 2010, 110 (1), pp 205-239, the contents of which are incorporated herein by reference.
  • the dielectric layer preferably comprises an organic material.
  • Preferred inorganic materials include BaTiOs, SiTi0 3 , SiCE, SiNx and spin-on-glass (SOG).
  • Preferred organic materials are organic polymers.
  • Exemplary polymers are, polyvinylpyrrolidine (PVP), acrylates such as polymethylmethacrylate (PMMA) and benzocyclobutanes (BCBs), poly(vinyl cinnamate) P(VCn), and partially fluorinated or perfluorinated polymers, for example poly(vinylidene fluoride-co-hexafluoropropylene) P(VDF-HFP), P(VDF-TrFE-CTFE), and polymers comprising or consisting of tetrafluoroethene repeat units.
  • the polymer may or may not be crosslinked.
  • the dielectric layer may consist of a polymer.
  • the dielectric layer may be a polymer / inorganic composite, for example as described in Materials 2009, 2(4), 1697-1733, the contents of which are incorporated herein by reference.
  • the inorganic material of the composite may be in the form of nanoparticles.
  • the inorganic material of the composite may have a dielectric constant of at least 5, at least 10 or at least 20.
  • the OTFT gas sensor may comprise more than one dielectric layer, optionally a dielectric bilayer in which a first dielectric layer in direct contact with the organic semiconducting layer comprises a material having a lower dielectric constant than a material of a second dielectric layer spaced apart from the organic semiconducting layer by the first dielectric layer.
  • the dielectric layer of a top-gate OTFT gas sensor comprises a gas- permeable material, preferably an organic material, more preferably a polymer material, which allows permeation through the dielectric layer of the gas or gases to be sensed.
  • the top-gate OTFT gas sensor has a single dielectric layer between the gate electrode and the semiconducting layer.
  • the top-gate OTFT gas sensor has more than one dielectric layer between the gate electrode and the semiconducting layer, each dielectric layer being permeable to the or each target gas.
  • the dielectric material may be deposited by thermal evaporation, vacuum processing or lamination techniques as are known in the art.
  • the dielectric material may be deposited from solution using, for example, spin coating or ink jet printing techniques and other solution deposition techniques discussed above with respect to the semiconductor layer.
  • the dielectric material should not be dissolved if an organic semiconductor is deposited onto it from solution.
  • the organic semiconductor layer should not be dissolved if the dielectric is deposited from solution.
  • Techniques to avoid such dissolution include: use of orthogonal solvents for example use of a solvent for deposition of the organic semiconducting layer that does not dissolve the dielectric layer in the case of a bottom gate device or vice versa in the case of a top gate device; cross linking of the dielectric layer before deposition of the organic semiconductor layer in the case of a bottom gate device; or deposition from solution of a blend of the dielectric material and the organic semiconductor followed by vertical phase separation as disclosed in, for example, L. Qiu, et al., Adv. Mater. 2008, 20, 1141.
  • the thickness of the dielectric layer is preferably less than 2 micrometres, more preferably less than 500 nm.
  • OTFT gas sensors as described herein may be used in detection of esters, e.g. C 1-10 alkyl esters or C 1-10 alkanoate esters, optionally C 1-10 alkyl- C 1-10 alkanoate esters, e.g.
  • methyl octanoate ethyl acetate; ethyl butanoate; ethyl hexanoate; propyl acetate; butyl acetate; butyl butanoate; butyl hexanoate; pentyl acetate; hexyl acetate; hexyl butanoate; hexyl hexanoate; 2-methylpropyl acetate; 2-methylbutyl acetate; ethyl 2-methylbutanoate; butyl 2-methylbutanoate; and hexyl 2-methylbutanoate.
  • OTFT gas sensors and gas sensor systems as described herein may be used in an environment in which an ester, e.g. butyl acetate, is produced by a natural process, e.g. by fruit.
  • an ester e.g. butyl acetate
  • OTFT gas sensors and gas sensor systems as described herein may be used in an environment in which one or more gases, such as styrene and butyl acetate, are produced by a natural process, e.g. by fruit.
  • the fruit may be apples.
  • Fruit rot may be detected by detection of styrene.
  • a PEN substrate was baked in a vacuum oven and then UV-ozone treated for 30 seconds.
  • Source and drain contacts were deposited onto the substrate by thermal evaporation of 3 nm Cr followed by 40nm Au through shadow masks with channel length of 125 mm and a channel width of 4 mm.
  • a solution of 4-aminobenzene thiol (4ABT) was spin-coated onto the source and drain electrodes from an isopropyl alcohol solution (0.1 % v/v). After 2 minutes, the substrate and source and drain electrodes were rinsed with isopropyl alcohol.
  • Semiconducting Polymer 1 illustrated below, was deposited over the substrate by spin coating from a 1%w/v solution in 1,2,4-trimethylbenzene to a thickness of 40nm and dried at 100°C for 1 or lOmin in air.
  • the polymer dielectric Teflon ® AF2400 was spin coated from a 2.5 %w/v solution in a 50:50 v/v blend of fluorinated solvents FC43 and FC85 to a 300nm thickness and dried at 80°C for lOmin, after a 5 minute initial drying phase while spinning.
  • the gate was formed by thermal evaporation of Cr (3 nm) followed by A1 (200 nm) through a shadow mask to form a gate electrode having a comb structure with comb fingers of 125 microns width and gaps of 125 microns between fingers.
  • OTFT Gas Sensor Example 2 was prepared as described for OTFT Gas Sensor Example 1 except that a solution of 4-aminobenzenethiol and 4-fluorobenzenethiol (1:1 w/w) was deposited by spin-coating onto the source and drain electrodes rather than a solution of 4- aminobenzenethiol alone.
  • Comparative OTFT Gas Sensor was prepared as described for Gas Sensor Example 1 except that a solution of 4-fluorobenzenethiol (4FBT) was used in place of 4- aminobenzenethiol .
  • the OTFT gas sensors were pulsed for 100ms every 25 s at a drain and gate voltage of -4V to give a sensor current of >10nA and exposed to methyl hexanoate vapour by flowing a carrier gas (N2) through the headspace that formed above a reservoir of methyl hexanoate liquid. This flow was then diluted using a separate flow of N2 carrier gas to set the methyl hexanoate concentration to 3,000 ppm.
  • N2 carrier gas
  • OTFT Gas Sensor Examples 1 and 2 showed a much greater response in terms of change in drain current than the Comparative OTFT Gas Sensor. Without wishing to be bound by any theory, this may be due to hydrogen bonding between the amino group of OTFT Gas Sensor Examples 1 and 2 and the ester. Use of both 4ABT and 4FBT in OTFT Gas Sensor Example 2 resulted in less variability between OTFTs than for OTFT Gas Sensor Example 1

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  • Thin Film Transistor (AREA)

Abstract

L'invention concerne un capteur de gaz à transistor organique en couches minces pour mesurer un ester, par exemple de l'acétate de butyle, dans un environnement gazeux. La réponse du capteur de gaz à transistor organique en couches minces à l'environnement est utilisée pour déterminer la présence et/ou la concentration de l'ester dans l'environnement. Le capteur de gaz à transistor organique en couches minces comprend des électrodes de source et de drain (107, 109) en contact électrique avec une couche semi-conductrice organique (111), une électrode grille (103), et un diélectrique grille (105) entre la couche semi-conductrice organique et l'électrode grille. Une monocouche (113) contenant un groupe protique, par exemple un groupement amine, est liée à des surfaces des électrodes de source et de drain. Le capteur de gaz à transistor organique en couches minces permet à un ester dans l'environnement d'interagir avec le groupe protique, ce qui provoque une sortie/variation dans la sortie du capteur de gaz à transistor organique en couches minces. La mesure de l'ester peut être utilisée pour déterminer la maturité de fruits.
PCT/GB2020/050126 2019-01-21 2020-01-21 Transistor organique en couches minces doté d'un groupe protique sur des électrodes de source et de drain pour déterminer la présence et/ou la concentration d'ester WO2020152453A1 (fr)

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GBGB1900836.6A GB201900836D0 (en) 2019-01-21 2019-01-21 Organic thin film transistor gas sensor and method
GB1900836.6 2019-01-21
GB1902297.9A GB2580717A (en) 2019-01-21 2019-02-20 Organic thin film transistor gas sensor
GB1902297.9 2019-02-20

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GB2597267A (en) * 2020-07-17 2022-01-26 Sumitomo Chemical Co Thin film transistor gas sensor system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100176837A1 (en) * 2007-05-03 2010-07-15 The Regents Of The University Of California Ultra-thin organic tft chemical sensor, making thereof, and sensing method
US20120018706A1 (en) * 2008-12-08 2012-01-26 The Trustees Of The University Of Pennsylvania Organic semiconductors capable of ambipolar transport
KR101183920B1 (ko) * 2011-03-09 2012-09-21 국방과학연구소 탄소나노튜브 트랜지스터형 유기인 화합물 가스 탐지용 가스센서 및 그 제조방법
WO2016001095A1 (fr) 2014-06-30 2016-01-07 Cambridge Display Technology Limited Transistor organique
DE102014215492A1 (de) * 2014-08-06 2016-02-11 Robert Bosch Gmbh Sensor zum Erfassen zumindest einer chemischen Spezies und Verfahren zu dessen Herstellung
JP2016065746A (ja) * 2014-09-24 2016-04-28 富士フイルム株式会社 ガスセンサ、トランジスタ

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4028062C2 (de) * 1990-09-05 1994-09-22 Winter Gaswarnanlagen Gmbh U Gassensoranordnung mit FET mit unterbrochenem Gate
JP6322717B2 (ja) * 2014-09-24 2018-05-09 富士フイルム株式会社 ガスセンサ、有機トランジスタ
GB201719856D0 (en) * 2017-11-29 2018-01-10 Sumitomo Chemical Co Gas sensor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100176837A1 (en) * 2007-05-03 2010-07-15 The Regents Of The University Of California Ultra-thin organic tft chemical sensor, making thereof, and sensing method
US20120018706A1 (en) * 2008-12-08 2012-01-26 The Trustees Of The University Of Pennsylvania Organic semiconductors capable of ambipolar transport
US8686404B2 (en) 2008-12-08 2014-04-01 The Trustees Of The University Of Pennsylvania Organic semiconductors capable of ambipolar transport
KR101183920B1 (ko) * 2011-03-09 2012-09-21 국방과학연구소 탄소나노튜브 트랜지스터형 유기인 화합물 가스 탐지용 가스센서 및 그 제조방법
WO2016001095A1 (fr) 2014-06-30 2016-01-07 Cambridge Display Technology Limited Transistor organique
DE102014215492A1 (de) * 2014-08-06 2016-02-11 Robert Bosch Gmbh Sensor zum Erfassen zumindest einer chemischen Spezies und Verfahren zu dessen Herstellung
JP2016065746A (ja) * 2014-09-24 2016-04-28 富士フイルム株式会社 ガスセンサ、トランジスタ

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
BESAR ET AL.: "Printable ammonia sensor based on organic field effect transistor", ORGANIC ELECTRONICS, vol. 15, no. 11, November 2014 (2014-11-01), pages 3221 - 3230, XP029076497, DOI: 10.1016/j.orgel.2014.08.023
CHEM. REV., vol. 110, no. 1, 2010, pages 205 - 239
CONGCONG ZHANG ET AL: "Organic field-effect transistor-based gas sensors", CHEMICAL SOCIETY REVIEWS, vol. 44, no. 8, 2 March 2015 (2015-03-02), UK, pages 2087 - 2107, XP055327029, ISSN: 0306-0012, DOI: 10.1039/C4CS00326H *
FENG ET AL.: "Unencapsulated Air-stable Organic Field Effect Transistor by All Solution Processes for Low Power Vapor Sensing", SCIENTIFIC REPORTS, vol. 6, pages 20671
ISLAM S ET AL: "Chitin and Chitosan: Structure, Properties and Applications in Biomedical Engineering", JOURNAL OF POLYMERS AND THE ENVIRONMENT, SPRINGER NEW YORK LLC, US, vol. 25, no. 3, 18 October 2016 (2016-10-18), pages 854 - 866, XP036298254, ISSN: 1566-2543, [retrieved on 20161018], DOI: 10.1007/S10924-016-0865-5 *
J DIXONE HEWETT: "Factors affecting apple aroma/flavour volatile concentration: a review", NEW ZEALAND JOURNAL OF CROP AND HORTICULTURAL SCIENCE, vol. 28, 2000, pages 155 - 173
L. QIU ET AL., ADV. MATER., vol. 20, 2008, pages 1141
LINRUN FENG ET AL: "Unencapsulated Air-stable Organic Field Effect Transistor by All Solution Processes for Low Power Vapor Sensing", SCIENTIFIC REPORTS, vol. 6, no. 1, 10 February 2016 (2016-02-10), XP055524292, DOI: 10.1038/srep20671 *
M. ESPINO-DIAZ ET AL.: "FOOD TECHNOL BIOTECHNOL.", BIOCHEMISTRY OF APPLE AROMA: A REVIEW, vol. 54, no. 4, December 2016 (2016-12-01), pages 375 - 397
MATERIALS, vol. 2, no. 4, 2009, pages 1697 - 1733
PHAN, NT.KIM, KH.JEON, EC. ET AL.: "Analysis of volatile organic compounds released during food decaying processes", ENVIRON MONIT ASSESS, vol. 184, 2012, pages 1683, Retrieved from the Internet <URL:https://doi.org/10.1007/s10661-011-2070-2>
ZHANG ET AL.: "Organic Field-Effect Transistors-Based Gas Sensors", CHEM. SOC. REV., vol. 44, 2015, pages 2087 - 2107

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