EP2612138A1 - Capteur nano-carbone et procédé de fabrication d'un capteur - Google Patents

Capteur nano-carbone et procédé de fabrication d'un capteur

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Publication number
EP2612138A1
EP2612138A1 EP11764120.9A EP11764120A EP2612138A1 EP 2612138 A1 EP2612138 A1 EP 2612138A1 EP 11764120 A EP11764120 A EP 11764120A EP 2612138 A1 EP2612138 A1 EP 2612138A1
Authority
EP
European Patent Office
Prior art keywords
layer
sensor
graphene
mediation
bio
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.)
Withdrawn
Application number
EP11764120.9A
Other languages
German (de)
English (en)
Inventor
Georg Duesberg
Martin Hegner
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.)
College of the Holy and Undivided Trinity of Queen Elizabeth near Dublin
Original Assignee
College of the Holy and Undivided Trinity of Queen Elizabeth near Dublin
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 College of the Holy and Undivided Trinity of Queen Elizabeth near Dublin filed Critical College of the Holy and Undivided Trinity of Queen Elizabeth near Dublin
Priority to EP11764120.9A priority Critical patent/EP2612138A1/fr
Publication of EP2612138A1 publication Critical patent/EP2612138A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table
    • H01L29/1606—Graphene

Definitions

  • the invention relates to the use of carbon nano-structures as sensor devices . More particularly, the invention relates to the use of graphene layers in a sensor device. Background to the Invention
  • Nano-carbon structures and in particular graphene, exhibit unique mechanical and electrical properties.
  • Many studies have been performed examining the use of carbon- nano tube (CNT) networks as (flexible) .
  • the interest in the field has lead to the establishment of many research groups and indeed start-up companies in the last few years .
  • CNTs carbon nanotubes
  • Label-free detection methods have been used in genomic, proteomic, and cell growth sensors.
  • label-free cantilever-array sensors have been used to detect human RNA (Zhang, J., Lang, H. P., Bietsch, A., Huber, F., Certa, U., Guntherodt, H . -J . , Hegner, M.* Gerber, Ch. (2006) Rapid and label-free nanomechanical detection of biomarker transcripts in human RNA Nature Nanotechnology, 1 ,214-220), interactions between transmembrane protein receptors and their ligands (Braun, T., Ghatkesar, M.K., Backmann, N.
  • the sensitivity of graphene is more sensitive than single walled carbon nano-tubes (SWCNTs) and nano-wires (NWs), and indeed first measurements on graphene devices have shown single molecule detection on a gated graphene device (Schedin, F . ; Geim, A. K.; Morozov, S. V.; Hill, E. W. ; Blake, P.; Katsnelson, M. I.; Novoselov, K. S. Nature Materials 2007, 6, 652-655) .
  • the versatility of graphene as a foundation for a sensor stems from its unique electronic structure, in that its ambipolarity property enables charge transport "chemical gating" of graphene to be monitored.
  • Patent Publication WO 2010/097518 describes a method of producing an electronic device comprising biological and electrical materials and an interface between the biological and electrical materials where self- assembly of proteins at a desired location on the device is utilised.
  • US Patent Publication number 2008/283875 describes a field effect transistor (FET) which includes a substrate, a source electrode and a drain electrode disposed on the substrate, where a channel for electrically connecting the electrodes is a carbon nanotubes .
  • FET field effect transistor
  • the document also describes a biosensor comprising the FET device.
  • US Patent Publication number 2010/025660 describes a semiconductor device comprising a source region, a drain region and a gate layer comprising carbon nanotubes and/or graphene .
  • a sensor device comprising: a first layer of graphene providing an interface; and a second layer of at least one bio-compatible component, wherein the first layer is functionalised by anchoring of the at least one bio-compatible component of the second layer to the first layer.
  • a further advantage of the present invention is the provision of label-free, highly selective detection of analytes ranging from gas, liquids, and bio-molecules, and also analysing cell growth in in vitro culture conditions.
  • the advantage provides devices which can test viability of cells (i.e. prokaryotes and eukaryotes) under certain growth conditions (sterility of solution, preservative tests, production control) in life and food science applications through detection on the graphene interfaces of the present invention.
  • the devices have application in diagnostics, Q&S testing in industrial samples (quick test for contamination, for resistance), environmental control in healthcare facilities such as hospitals, and in the Bio- pharma industry such as food production controls .
  • the first layer of graphene may be a conducting semiconduction layer or a thin conducting layer composed of ( nano- ) carbon and/or a thin (monolayer) of sp2 hybridised carbon .
  • the bio-compatible component of the second layer directly functionalises the graphene first layer .
  • a mediation layer is adapted to integrate between the first layer and second layer .
  • the mediation layer is functionalised by the anchoring of the at least one bio-compatible component of the second layer.
  • the mediation layer is a biocompatible polymer selected from the group comprising a dielectric polymer, a polymer adapted to store electrolytes, a polymer adapted to store a prokaryote and/or eukaryote cell growth medium, or an ion exchange membrane .
  • the polymer may be suitable for polymer imprinting.
  • a polymer suitable for polymer imprinting is taken to mean a molecular imprinted polymer (MIP) , which is a plastic polymer formed in the presence of a molecule that is extracted afterwards, leaving an imprint of the molecule or complementary cavities behind.
  • MIP molecular imprinted polymer
  • the imprinted polymers demonstrate an affinity for the original molecule.
  • the process of polymer imprinting is well known to those skilled in the art.
  • the mediation layer may be a dielectric, such as, for example an oxide layer selected from the group comprising aluminium oxide, silicon oxide, Hafnium oxide, Tantalum oxide, or nitrides, or mixtures thereof.
  • the oxide layer is deposited by atomic layer deposition. In one embodiment, the oxide layer is further functionalised with at least one biocompatible component . In one embodiment the at least one bio-compatible component is selected from the group comprising single-stranded DNA, double-stranded DNA, ribonucleic acid (RNA) , amino acids, protein receptors, ligands, prokaryotic cells, or eukaryotic cells .
  • RNA ribonucleic acid
  • first layer of graphene providing an interface
  • second layer of at least one bio-compatible component wherein the first layer is functionalised by anchoring of the at least one bio-compatible component of the second layer to the first layer
  • a mediation layer is adapted to integrate between the first layer and second layer and wherein the first layer is sensitive to electrolyte and/or gas concentrations .
  • the mediation layer comprises a nutrition media for cells and said sensor comprises means for sensing changes in the composition of a liquid phase and/or solid phase within the mediation layer.
  • the changes in the media composition can be detected by the first layer due to changes in electrical signals.
  • the term "nutrition media for cells” incorporates all growth media for cells (mammalian and/or bacteria cells) known to a person skilled in the art, for example, Luria Broth (liquid phase), Agar (solid phase), mammalian cell growth media (liquid phase) and the like known.
  • the liquid layer in this instance is the electrolyte source which can provide not only ionic substances which can affect the graphene sensing but also provides polar, apolar molecules and other non-charged molecules.
  • the graphene layer is adapted to cooperate an electrode.
  • the senor comprises two or more electrodes to form a transistor junction such that the graphene layer forms a channel to provide a high sensitivity sensing area.
  • the bio-compatible component comprises a single molecule.
  • the senor comprises a nano-carbon device.
  • a device for label-free detection comprising the sensor of the present invention.
  • a sensor device comprising :
  • first layer of graphene providing an interface
  • second layer of at least one component wherein the first layer is functionalised by anchoring of the at least one component of the second layer to the first layer.
  • a sensor device comprising:
  • first layer of a carbon-based material providing an interface
  • second layer of at least one bio-compatible component wherein the first layer is functionalised by anchoring of the at least one bio-compatible component of the second layer to the first layer
  • a sensor device comprising:
  • a second layer of at least one component wherein the first layer is functionalised by anchoring of the at least one component of the second layer to the first layer.
  • first layer of graphene providing an interface
  • second layer of at least one biocompatible component wherein the first layer is functionalised by anchoring of the at least one biocompatible component of the second layer to the first layer.
  • the graphene layer may have a thickness of between about 0.1 nm to about 100 nm, preferably between about 0.1 nm to about 50 nm, more preferably between about 0.1 nm to about 25 nm, between about 0.1 nm to about 15 nm, and ideally between about 0.1 nm to about 10 nm.
  • the first layer is functionalised by anchoring of the at least one biocompatible component of the second layer to the first layer .
  • a mediation layer adapted to integrate between the first layer and second layer, wherein the first layer is sensitive to electrolyte and/or gas concentrations .
  • Figure 1 illustrates a biosensor of the present invention having, for example, receptor molecules for any one of chemical, genomic or proteomic analysis coupled directly or indirectly to a mediation layer deposited onto graphene by thin film deposition techniques such as atomic layer deposition (ALD) or ink-jet plotting;
  • ALD atomic layer deposition
  • ALD ink-jet plotting
  • Figure 2 illustrates a schematic representation of various means to functionalize a graphene interface with a biological molecule/cell of interest: (I) direct adsorption of the bio-molecule of interest; (II) functionalizing a receptor molecule of interest with a chemical group and anchoring the receptor molecule to graphene chelation with a specific organic tag (for example, a HIS-tag) bound to graphene by pi- stacking via a nucleotide base; (III) a receptor of interest having multiple binding sites is modified with an affinity tag (for example, biotin-avidin ) , and anchored to a functional graphene via an intermediate receptor; and (IV) a thin mediation layer, for example a functional polymer layer, overlying the graphene may be filled with electrolytes which serves as a (cell- specific) medium reservoir for cell growth (prokaryotes and eukaryotes provides label-free detection enabled through electrical detection;
  • a specific organic tag for example, a HIS-tag
  • Figure 3 is an electronmicrograph of a device of the present invention.
  • Figure 4 is graph of Current ( UA ) versus Gate Voltage (V) produced by the graphene sensor of Figure 3 (IV) where the active graphene area was contacted with gold electrodes by electro-beam lithography.
  • Figure 5 illustrates a schematic diagram of a biosensor of the present invention wherein metal electrodes contacting an underlying graphene layer act as a sensor device with (a) bacteria proliferation occurring within a dosed volume of LB medium and (b) bacteria proliferation occurring on a thin agar layer, filled with a nutritive medium;
  • Figure 6 illustrates a graph showing a gate sweep performed using a back-gated graphene label-free filed effect transistor (FET) device showing that with exposure to LB medium there is a shift in the Dirac curve towards the negative bias voltage;
  • FET field effect transistor
  • Figure 7 is a schematic showing the production and microfabrication of graphene.
  • (a) CVD growth of graphene on copper foil in a tube furnace (b) graphene is attached to SiC>2/Si by attaching to a support layer of PMMA and thermal release tape and transferring by a combination of heat and pressure, (c) after transfer to Si0 2 /Si substrate a Ni protection layer is patterned on the graphene, (d) an oxygen plasma removes the unprotected graphene and the Nickel is removed by HC1 etching.
  • Figure 8 illustrates (a) Example Raman spectrum of CVD grown graphene after transfer; (b) Controlled deposition of small volumes of LB/glycerol medium is shown to be accurate by optical microscopy; (c) The p- type behaviour of the pristine graphene is observed and a clear increase in hysteresis is noted upon measurement of LB. A shift in gate dependency with LB concentration is also noted. The glycerol is added to reduce droplet evaporation and is maintained at the same concentration in each case; and (d) A change in resistance with LB concentration is noted using two- probe measurements on the graphene FET; and
  • Figure 9 illustrates that micro-dispensing of 50%LB/25% glycerol medium containing E.-coli demonstrates that it is feasible to guide proliferation to the graphene sensor region.
  • An SEM image shows the graphene sensor and contacts at 80° tilt with a dense circular pattern of adhered bacteria fixed using a dehydration protocol and shown in (b) at a higher magnification image.
  • Nano-carbon structures and in particular graphene, exhibit unique mechanical and electrical properties.
  • Many studies have shown the use of carbon nano-tube (CNT) networks as (flexible) .
  • Graphene has been shown to have superior sensitivity, being able to detect single molecules. Therefore it can potentially lead to ultra-low noise sensors due to the change of charge carried in 2- dimensional (2D) graphene flakes, ideally measured in a gated shift of the Dirac point .
  • Figure 1 illustrates a general embodiment of the present invention.
  • receptor molecules of interest are introduced on or in the vicinity of a graphene sheet.
  • Receptor molecules for chemicals, genomic or proteomic analysis will be coupled directly or indirectly to a mediation layer deposited onto graphene by thin film deposition techniques such as atomic-layer deposition (ALD) or ink-jet plotting.
  • the mediation layer allows the introduction of specific receptors without destroying the ultra-sensitivity of graphene, in contrast to the indirect functionalisation methods .
  • a current flows from a sink (S) to a drain (D) across the graphene sheet and, optionally, measured by a bottom gate (G) embedded in a substrate.
  • any depletion in the concentration of the analyte of interest in the fluid following interaction with the receptor molecules adhered to the mediation layer causes a change in the charge distribution in the nano- fluidic channel.
  • the change in charge distribution is directly transferred to the graphene sheet underlying the mediation layer, which in turn modulates current transport through the device and a signal is generated.
  • nucleic acids for example deoxyribonucleic acid (DNA) , ribonucleic acid (RNA) , a layer of single stranded (ss) or double stranded (ds) DNA are immobilised on the graphene sheet.
  • the ssDNA are immobilised as a layer on the graphene sheet.
  • a sample containing ssDNA is passed over the sensor, complimentary ssDNA in the sample bind to the immobilised ssDNA on the graphene sheet.
  • the hybridisation of ssDNA sequences changes the charge distribution at the surface of the graphene sheet.
  • the change in charge distribution modulates the current transport through the device and is detected by the transfer characteristics through the graphene channel. This can be either seen in a change in resistance of the channel in two point configuration.
  • the change in the transfer characteristics (e.g. Dirac point shift) of the 3- terminal device (field effect transistor) can de detected (see Fig 4)
  • the sensor as illustrated in Figure 1 may be produced with a graphene sheet having a thickness of between about 0.1 nm to about 10 nm, the sensor synthesised by the following method :
  • the substrate may be any one or more of the group comprising silicon oxide, aluminium oxide, or platinum;
  • Metal for example, Ni, Pd, Pt, Au, and/or Ag
  • carbon contact deposition for example, Ni, Pd, Pt, Au, and/or Ag
  • the graphene sheet is overlaid with a mediation layer .
  • the mediation layer is functionalised by site-specific immobilisation of receptors.
  • the interaction of the receptor with the ligand directly transduces a shift in electrical conductivity of the underlying graphene sheet .
  • FIG. 2 there is illustrated a selection of methods to functionalize a graphene sheet interface with biocompatible buffer layers which enables anchoring of biological molecules of interest (e.g. receptors or ligands, nucleic acids, proteins (on a molecular scale), and whole cells (e.g. microorganisms and eukaryotic cells)) .
  • biological molecules of interest e.g. receptors or ligands, nucleic acids, proteins (on a molecular scale), and whole cells (e.g. microorganisms and eukaryotic cells)
  • the functionalisation of the graphene layers with bio- molecules can have four different routes :
  • a receptor with multiple binding sites is anchored to the functional graphene layer via a modifying reaction such as covalent linkage .
  • a modifying reaction such as covalent linkage
  • covalent linkage is a biotinylation reaction where the protein of interest is tagged with biotin which has an affinity for avidin and then anchored to an intermediate receptor.
  • a thin mediation layer can be a polymer layer filled with electrolytes which serves as a medium reservoir for cell growth (prokaryotes and eukaryotes), which can be selective for certain cells . Upon cell growth the media will change its composition (pH and/or bio-molecule concentration) which can be detected by the underlying graphene sheet due to changes in the electrical signals .
  • the above-described devices provide label-free detection enabled through electrical detection.
  • the advantage over silicon nanowires or carbon nanotubes is provided by the fact that the large sheets of graphene can be synthesized and subsequently structured into individual active subunits for array read-out .
  • the interface of the graphene sheet is covered with a buffer (polymer) layer which acts as a reservoir of nutritive molecules required for cell proliferation. Individual cells are settled on top of the buffer layer. During subsequent cell proliferation, the dividing cells use the nutritive molecules residing in the buffer layer. This leads to a shift in electrically active compounds nucleic acids, amino acids or sugars from the buffer layer into the dividing cells and subsequently leads to a shift in electrical conductivity in the underlying graphene.
  • a buffer polymer
  • Such a device enables direct label-free detection of receptor-ligand interaction and the direct growth detection of cells residing on top of a buffer layer.
  • Figures 3 and 4 illustrate the device as described in Figure 2 (IV) above.
  • Figure 3 shows a graphene sheet (B) between two electrodes (S) and (D) .
  • Figure 4 is a graph of Current (UA) versus Gate Voltage (V) which demonstrates the device as described in Figure 2 (IV) and shown in Figure 3.
  • the graphene sheets (B) grown by chemical vapour deposition (CVD) were contacted with gold electrodes (S and D) with e- beam lithography.
  • Figure 3 shows a parabolic shape typical for high quality multi layered graphene ( ⁇ pristine) .
  • Dirac point Its minimum point is called the Dirac point and lies at a gate voltage (V or V g ) of + 10V.
  • V or V g gate voltage
  • LB Luria Broth
  • the Dirac point shifts to more negative voltages because of the interaction of the electrolytes in the LB with the graphene.
  • the minima lay at - 17V, -34V and 43 V for a 1% (A), 10% (T) , and 100% ( ⁇ ) LB solution (nutritive solution), respectively.
  • a concentration of LB solutions can be measured by a three terminal graphene device with high accuracy, since the shift in gate voltage can be measured in the mV range .
  • Figure 5 illustrates a device 1 of the present invention where the interface of the graphene sheet B is covered with a buffer layer 2 ( (a) LB broth 3 and (b) a thin agar layer 5), which acts as a reservoir of nutritive molecules required for cell proliferation, in this instance, bacteria cell proliferation.
  • the graphene sheets (B) are contacted by electrodes 6.
  • Individual cells 4 are settled on top of the buffer layer 2.
  • the dividing cells use the nutritive molecules residing in the buffer layer 2. This leads to a shift in electrically active compounds nucleic acids, amino acids or sugars from the buffer layer 2 into the dividing cells and subsequently leads to a shift in electrical conductivity in the underlying graphene B.
  • Such a device enables direct label- free detection of receptor-ligand interactions and the direct growth detection of cells residing on top of a buffer layer .
  • the robust nature of the graphene FETs illustrated in Figure 5 allows repeated cleaning and re-use while the output is a simple electrical resistance measurement in the kQ range .
  • sensor devices as described in Figure 2 (IV) and Figure 5 above, are manufactured on 15 ⁇ 15 mm pieces of p-doped (Boron) silicon ⁇ 100> with a 300 nm layer of S1O 2 from Si- Mat Silicon Materials, Germany and cut using the Disco DAD 3220 wafer dicer. Samples are cleaned prior to micro- fabrication using ultrasonication in HPLC grade acetone, ultrasonication and rinse in HPLC grade propan-2-ol and subsequent drying in a rapid flow of filtered, dry nitrogen. An oxygen plasma treatment is also carried out to remove organic contamination using the Diener PICO barrel asher .
  • UV lithography was designed in-house and created using the Heidelberg DWL 66FS direct writing system. UV lithography was carried out with the OAI Mask Aligner using Microposit S1813 positive photo resist and MF319 developer (both from Rohm and Haas Electronic Materials) . Metal sputter deposition was carried out using the Gatan 682 Precision Etching Coating System at a rate of 0. lAs -1 . After standard polymer lift-off procedures, residual polymer was removed by oxygen plasma treatment except when graphene was present, when solvent cleaning alone was used.
  • Graphene is transferred from metal foil to the substrate as follows.
  • a layer of Poly (methyl methacrylate) (PMMA) (Mr- I 35 K PMMA from Microresist Technology GmBH) was spin coated on top of graphene film/copper foil pieces .
  • Thermal release tape was adhered on top of this PMMA support film and the copper was then etched by floating the sample in etchant (0.25 M FeCl 3 + 0.2 M HC1) .
  • the resulting layered film of thermal release tape/PMMA/graphene was cleaned with DI water, dried and placed on to the substrate (as shown in Figure 7b) .
  • E. coli CIP 53.126 was obtained from Collection de l'Institut Pasteur (Paris, France) . Overnight cultures were prepared (200 rpm, 35 °C , 15-18 h) in LB (1% NaCl, 1% Tryptone, 0.5% Yeast extract) from single colonies of E. coli. 1 mL of the overnight cultures were transferred into 30 mL of 50% LB, 25% glycerol, 25% DI water and cultured (200 rpm, 35 °C) for 110 min in order to reach a logarithmic growth rate. Glycerol was added to ensure droplets did not evaporate prior to measurement .
  • LB medium both with and without cells were dosed using an Autodrop micro-dispensing system from Microdrop Technologies and a nozzle with a diameter of 50 ym.
  • Raman spectroscopy was carried out using a Horriba Jobin Yvon LabRam HR system and a line of 632.8 nm.
  • Scanning electron microscopy (SEM) was carried out using the Zeiss ULTRA Plus in the Advanced Microscopy Laboratory, CRANN, Trinity College Dublin. Prior to SEM imaging, bacteria were fixed by soaking in 5 % v /v glutaraldehyde solution in 0.05 M phosphate buffer (pH7) and incubated at room conditions with gentle agitation for 3-4 h. Glutaraldehyde was then removed by 6 successive washes in fresh 0.05 M phosphate buffer, each of 10 minutes duration. Samples were subsequently dehydrated with a sequence of 10 minute rinses in 10, 30, 50, 70, 90, 100, 100% v v ethanol .
  • the graphene used in present invention was grown by chemical vapour deposition (CVD) and all patterning was carried out by optical lithography.
  • the CVD growth was carried out on 15 x 15 mm samples of copper foil in a tube furnace, as indicated in Figure 7a.
  • the copper can be removed by etching with FeCl 3 .
  • Transfer of graphene to Si0 2 /Si substrates is completed by applying pressure through the tape and PMMA support layers, pressing the graphene surface onto the substrate as indicated in Figure 7b. Heat applied through the substrate allows easy release of the thermal release tape leaving behind the PMMA/graphene layers with the graphene adhering to the substrate very strongly by van der Waals forces .
  • the PMMA can be removed with solvent cleaning.
  • An alternative method which can be used involves applying the PMMA support layer to the graphene film/copper foil pieces and etching as before at the liquid-air interface, leaving a graphene/PMMA layer floating on the surface. This is carefully transferred to the substrate surface through dip-coating and the same solvent cleaning steps occur to remove PMMA.
  • the substrates have been pre- structured by UV lithography with distinct, chromium alignment marks to enable a sequence of UV lithography patterning steps to occur that lead to metal-contacted graphene strips with good adhesion to the substrate.
  • a sacrificial masking pattern of nickel is formed to protect the areas required for the devices and the uncovered graphene is removed by an oxygen plasma.
  • Nickel is completely removed by an acid etch with 1 M HC1 and the remaining graphene strips are contacted by four Ni/Au electrodes using a final UV lithography step.
  • the contacted samples can then be probed directly using a needle prober or wire-bonded to a chip carrier for electrical measurements.
  • a range of alignment marks were used for accurate positioning of all layers and a design which can be directly incorporated into an inkjet dosing system .
  • the gate voltage behaviour and the scale of resistances recorded for graphene prepared with this technique are illustrated in Figure 8.
  • An example Raman spectrum of CVD grown graphene on copper and transferred to S1O 2 is shown in Figure 8a.
  • the G and 2D band are clearly visible.
  • the small bandwidth and the high 2D/G ratio is indicative of single layer graphene.
  • Figure 9a shows an SEM image of the dense drying pattern surrounding a graphene FET device 1 of the present invention made up of the E. coli 10 shown in more detail in the SEM image of Figure 9b. Imaging of the control and incubated samples shows an increase in cells/unit area by a factor of 8.6 over the course of 1 day.
  • E. coli 10 were micro-dispensed in a buffer layer 2 onto the graphene sheet B of the sensor device 1 of the present invention. Comparisons were made between a device in an ambient atmosphere where the droplet is allowed to dry and a device maintained in an incubator for 1 day. The results show (i) the survival of the E. coli through the dispensing protocol, (ii) no obvious ill effects of the substrate or possible contaminants from fabrication processes and (iii) bacteria proliferation around the sensor area.
  • the sensors have a significant advantage in performance, reaction time, cost, and stability over current approaches.
  • the term “layer” should be interpreted broadly as to comprise a sheet or platform or any surface that can support the sensor of the present invention and should be afforded the widest possible interpretation. Those terms which can be interpreted broadly to be comprised in the term “layer” are also interchangeable with one another .

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Abstract

L'invention concerne un dispositif de capteur comprenant une première couche de graphène formant une interface; et une seconde couche d'au moins un composant biocompatible, la première couche étant fonctionnalisée par ancrage du au moins un composant biocompatible de la seconde couche à la première couche et une couche de médiation étant apte à s'intégrer entre la première couche et seconde couche et la première couche étant sensible aux concentrations d'électrolyte et/ou de gaz.
EP11764120.9A 2010-09-03 2011-09-05 Capteur nano-carbone et procédé de fabrication d'un capteur Withdrawn EP2612138A1 (fr)

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EP11764120.9A EP2612138A1 (fr) 2010-09-03 2011-09-05 Capteur nano-carbone et procédé de fabrication d'un capteur

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EP10175283A EP2426487A1 (fr) 2010-09-03 2010-09-03 Capteur de nano-carbone et procédé de fabrication d'un capteur
PCT/EP2011/065337 WO2012028748A1 (fr) 2010-09-03 2011-09-05 Capteur nano-carbone et procédé de fabrication d'un capteur
EP11764120.9A EP2612138A1 (fr) 2010-09-03 2011-09-05 Capteur nano-carbone et procédé de fabrication d'un capteur

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EP2612138A1 true EP2612138A1 (fr) 2013-07-10

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