CN113311048B - Nanofluidic field effect transistor and preparation method and application thereof - Google Patents

Nanofluidic field effect transistor and preparation method and application thereof Download PDF

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CN113311048B
CN113311048B CN202110570151.0A CN202110570151A CN113311048B CN 113311048 B CN113311048 B CN 113311048B CN 202110570151 A CN202110570151 A CN 202110570151A CN 113311048 B CN113311048 B CN 113311048B
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field effect
membrane
film
porous membrane
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CN113311048A (en
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吴增强
华宇
潘忠芹
胡玉林
王娇娇
王金玉
汪晓明
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Nantong University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4146Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS involving nanosized elements, e.g. nanotubes, nanowires

Abstract

The invention provides a nano-fluidic field effect tube and a preparation method and application thereof, relating to the technical field of nano-fluidic and electrochemistry, comprising the following steps: the inner surface of the nano pore canal is provided with a first nano porous membrane with positive charges, a second nano porous membrane with negative charges and an electrode; and respectively combining the two surfaces of the second nano porous film with the first nano porous film, or respectively combining the two surfaces of the first nano porous film with the second nano porous film to construct the nano-fluidic field effect transistor with an NPN or PNP structure. The invention utilizes the ion selective transmission characteristic of the nano channel, combines gate potential control to change the surface charge density of part of the nano channel to realize signal amplification under the condition of low gate potential, solves the problem that the existing field effect transistor can not realize detection under high ion intensity, successfully realizes the Sigmoid response of the ion current signal of the nano channel, and can be used as a controllable unit component for subsequent logic control and a switch component of an artificial neural network.

Description

Nanofluidic field effect transistor and preparation method and application thereof
Technical Field
The invention relates to the technical field of nanofluidics and electrochemistry, in particular to a nanofluidic field effect transistor and a preparation method and application thereof.
Background
The existing field effect tube analysis devices are all constructed based on solid-state semiconductors, and the current amplification effect of the field effect tube is utilized to amplify the signals of substances in analysis and detection so as to realize detection of low-concentration substances. Along with the development of two-dimensional nano materials, the problem of miniaturization of the field effect transistor is solved, and the field effect transistor is gradually applied to a wearable detection device.
However, the signal-to-noise ratio of the fet is inversely proportional to the dynamic response range of the fet itself, i.e., when the dynamic detection range of the fet increases, the signal-to-noise ratio of the detection signal decreases. Therefore, to ensure the signal-to-noise ratio of the fet, it is often necessary to define the dynamic response range of the fet. In order to obtain a sufficient response signal, the problem of the size of an electric double layer of the field-effect tube must be considered, that is, when the size of a detection substance is equal to the size of the field-effect tube, the field-effect tube can obtain the sufficient response signal, which further limits the detection application of the field-effect tube under high ionic strength, especially in the detection of biological samples, because the high ionic strength causes the thickness of the electric double layer of the field-effect tube to be reduced to about 1 nanometer, the detection signal of the field-effect tube is further weakened, and thus the detection accuracy of the field-effect tube is reduced, the common solution is to modify the field-effect tube by adopting polyelectrolyte to improve the response characteristic under the high ionic strength, but the polyelectrolyte modification causes another problem, that is, the field-effect tube after the polyelectrolyte modification needs to obtain higher current amplification efficiency under higher gate potential (> 20V). Such high gate potentials cannot be used for biomolecular detection, especially protein detection.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a nanofluidic field effect transistor, which utilizes the ion selective transmission characteristic of a nano channel and combines gate potential control to change the surface charge density of part of the nano channel so as to realize signal amplification under the condition of low gate potential.
The second purpose of the invention is to provide a preparation method of the nanofluidic field effect transistor.
The invention further aims to provide an application of the nanofluidic field effect transistor or the artificial neural network switching device in biomolecule detection.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the present invention provides a nanofluidic field effect transistor, comprising: a first nanoporous membrane, a second nanoporous membrane, and an electrode; the inner surface of the nano pore canal in the first nano porous membrane is provided with positive charges, and the inner surface of the nano pore canal in the second nano porous membrane is provided with negative charges; the electrodes include a gate electrode and a driving electrode;
the two surfaces of the second nano-porous film are respectively combined with the first nano-porous film, and the gate electrode is arranged on the second nano-porous film; or, the two surfaces of the first nano porous film are respectively combined with the second nano porous film, and the gate electrode is arranged on the first nano porous film to construct the nano-fluidic field effect tube with an NPN or PNP structure.
Further, the first nano-porous membrane is a modified PET nano-porous membrane, a modified PC nano-porous membrane or a polyaniline membrane, preferably a PET nano-porous membrane.
Further, the second nano-porous membrane is a Nafion membrane or an unmodified PET nano-porous membrane.
Further, the size of the nano pore canal in the first nano porous membrane is 20-50nm; the thickness of the first nano porous film is 10-50 mu m;
the size of the nano pore canal in the second nano porous membrane is 20-50nm; the second nanoporous film has a thickness of 10-50 μm.
Further, a conducting wire is led out from the second nano porous film by adopting conductive silver paste to form a gate electrode; or, leading out a wire from the first nano porous film by adopting conductive silver paste to form a gate electrode;
the driving electrode adopts an Ag/AgCl electrode.
Further, the nano pore canal in the first nano porous membrane is conical.
In a second aspect, the present invention provides a method for preparing a nanofluidic field effect transistor, including the following steps:
(a) Providing a PET nano porous membrane, and then modifying the PET nano porous membrane to enable the inner surface of a nano pore canal to have positive charges, or providing a polyaniline membrane;
(b) Coating a layer of Nafion film or overlapping a layer of unmodified PET nano porous film on the surface of the PET nano porous film or polyaniline film with positive charges on the inner surface of the nano pore canal obtained in the step (a), combining the Nafion film or the polyaniline film with the positive charges on the inner surface of the nano pore canal obtained in the other step (a), and applying a gate electrode on the Nafion film or the unmodified PET nano porous film to obtain the nano-fluidic field effect transistor with an NPN structure.
The invention also provides a preparation method of the nanofluidic field effect transistor, which comprises the following steps:
(a) Providing a PET nano porous membrane, and then modifying the PET nano porous membrane to enable the inner surface of a nano pore canal to have positive charges, or providing a polyaniline membrane;
(b) Providing an unmodified PET nanoporous membrane or Nafion membrane; and (c) superposing a layer of PET nano-porous membrane or a layer of polyaniline membrane with positive charges on the inner surface of the nano-pore canal obtained in the step (a) on the surface of the unmodified PET nano-porous membrane or the Nafion membrane, combining the PET nano-porous membrane or the Nafion membrane with the positive charges with the other unmodified PET nano-porous membrane or the Nafion membrane, and applying a gate electrode on the PET nano-porous membrane or the polyaniline membrane with the positive charges on the inner surface of the nano-pore canal to obtain the nano-fluidic field-effect transistor with the PNP structure.
Further, in step (a), the method of modifying in the first nanoporous film comprises:
firstly, immersing a first nano-porous membrane to be modified in a mixed solution of EDC (1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride) and NHS (N-hydroxysuccinimide sulfonate) for 30-60 minutes; the nanoporous membrane is then washed and then placed in a (2-aminoethyl) trimethylammonium chloride solution for more than 12 hours.
In a third aspect, the invention provides an application of the nanofluidic field effect transistor in biomolecule detection or preparation of an artificial neural network switching device.
The nano-fluidic field effect tube and the preparation method and application thereof have at least the following beneficial effects:
1. the invention utilizes the ion selective transmission characteristic of the nano channel (nano pore canal) and combines the gate potential control to change the surface charge density of part of the nano channel so as to realize the signal amplification under the condition of low gate potential.
2. The invention can realize 1000 times of current amplification efficiency (10 mM) under lower gate potential (< 2V), and 830 times of current amplification under high ion intensity (100 mM), thereby solving the problem that the existing field effect transistor can not realize detection under high ion intensity.
3. Through the control of the gate potential, the sigmoid response of the nano channel ion current signal is successfully realized, so that the nano channel ion current signal can be used as a controllable unit component for subsequent logic control and a switching component of an artificial neural network.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic longitudinal section view of a nanofluidic field effect transistor according to an embodiment of the present invention;
fig. 2 is a diagram of a detection device of a nanofluidic field effect transistor according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a current amplifying system of a nanofluidic field effect transistor according to an embodiment of the present invention, where a is a schematic diagram of a current amplifying system of a nanofluidic field effect transistor with a PNP structure, and b is a schematic diagram of a current amplifying system of a nanofluidic field effect transistor with an NPN structure;
fig. 4 is a response signal of different types of nanofluidic field effect transistors, wherein a is a response signal of the ionic current of the nanofluidic field effect transistor with a PNP structure under different gating potentials, and b is a response signal of the ionic current of the nanofluidic field effect transistor with an NPN structure under different gating potentials;
FIG. 5 shows the change of ion current under different gate potential and the current amplification efficiency under different concentrations of the nanofluidic field effect transistor, wherein a is the relation between the gate control current and the driving current of the PNP structure nanofluidic field effect transistor under the concentration of 10mM KCl, b is the relation between the current amplification efficiency and the gate control current of the PNP structure nanofluidic field effect transistor under the concentration of 10mM KCl, c is the relation between the current amplification efficiency and the gate control current of the PNP structure nanofluidic field effect transistor under the concentration of 100mM KCl, d is the relation between the gate control current and the driving current of the NPN structure nanofluidic field effect transistor under the concentration of 10mM KCl, e is the relation between the current amplification efficiency and the gate control current of the NPN structure nanofluidic field effect transistor under the concentration of 10mM KCl, and f is the relation between the current amplification efficiency and the gate control current of the NPN structure nanofluidic field effect transistor under the concentration of 100mM KCl;
fig. 6 is a relationship of an ion current response curve of an NPN nanofluidic field effect transistor along with a gate potential change, where a is a signal of the NPN nanofluidic field effect transistor Sigmoid response, b is a rectified response signal of the NPN nanofluidic field effect transistor, and c is a linear response signal of the NPN nanofluidic field effect transistor.
Icon: 1-PET nanoporous film; 2-PET nano porous membrane nano pore canal; 3-Nafion membrane; nano pore canal of 4-Nafion film; 5-gate electrode.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
At present, a field effect tube device based on nano fluid is not available, and in order to solve the problem that the existing field effect tube can not realize detection under high ionic strength, the invention constructs a field effect tube based on nano channel, comprising: a first nanoporous membrane, a second nanoporous membrane, and an electrode; the inner surface of the nano pore canal in the first nano porous membrane is provided with positive charges, and the inner surface of the nano pore canal in the second nano porous membrane is provided with negative charges; the electrodes include a gate electrode and a driving electrode; the two surfaces of the second nano porous film are respectively combined with the first nano porous film, and the second nano porous film is provided with a gate electrode; or, the two surfaces of the first nano porous film are respectively combined with the second nano porous film, and the first nano porous film is provided with a gate electrode to construct the nano-fluidic field effect tube with an NPN or PNP structure.
The first nanoporous membrane may be selected from a polyaniline membrane, a modified PET nanoporous membrane, or a modified PC nanoporous membrane.
The PET film is a porous film composed of a plurality of nano channels, and the preparation method is as follows: firstly, respectively injecting sodium hydroxide and oxalic acid solution at two sides of an ion track film, then applying 1 volt voltage at two sides of the film, controlling the size of a nano channel in the film to be about 20 to 50nm by controlling current, and modifying positively charged molecules in the PET film to enable the positively charged molecules to be positively charged.
Positively charged molecules include, but are not limited to, channel surface amination modifications, one typical modification method being as follows:
firstly, immersing a PET film to be modified in a mixed solution of EDC (1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride) and NHS (N-hydroxysuccinimide sulfonate) for 30-60 minutes; the nanoporous membrane is then washed and then placed in a (2-aminoethyl) trimethylammonium chloride solution for more than 12 hours.
Polyaniline membranes are positively charged porous membranes and do not require treatment.
In a preferred embodiment, the size of the nanopores in the first nanoporous film is from 20 to 50nm; the first nanoporous film has a thickness of 10-50 μm (e.g., 12 μm).
The second nanoporous membrane may be selected from a Nafion membrane or an unmodified PET nanoporous membrane.
Nafion membranes are negatively charged porous membranes with nanochannel sizes on the order of tens of nanometers. Conventional Nafion does not require processing.
The unmodified PET film is a negatively charged porous film.
In a preferred embodiment, the size of the nanopores in the second nanoporous film is from 20 to 50nm; the second nanoporous film had a thickness of 10 μm.
The nanofluidic field effect tube of the NPN structure can be any one of the following combination forms:
modified PET film (+) -Nafion film (-) -modified PET film (+); the middle is Nafion film, the two sides are modified PET film, the other is the same, and the charge property is shown in brackets.
Polyaniline film (+) -Nafion film (-) -polyaniline film (+);
modified PET film (+) -unmodified PET film (-) -modified PET film (+);
polyaniline film (+) -unmodified PET film (-) -polyaniline film (+).
The nano-fluidic field effect transistor with the PNP structure can be any one of the following combination forms:
unmodified PET film (-) -polyaniline film (+) -unmodified film PET (-);
nafion film (-) -modified PET film (+) -Nafion film (-);
nafion membrane (-) -polyaniline membrane (+) -Nafion membrane (-);
unmodified PET film (-) -modified PET film (+) -unmodified film PET (-).
As a preferred embodiment, as shown in fig. 1 and 2, the nanofluidic field effect tube is composed of a PET nano porous membrane 1, a Nafion membrane 3, an electrode and the like, wherein the size of a nano pore canal 2 of the PET nano porous membrane is 20-50nm, the nano pore canal 2 of the PET nano porous membrane is conical, and the inner surface of the nano pore canal 2 of the PET nano porous membrane is modified to have positive charges; the size of the nano pore canal 4 of the Nafion film is 20-50nm, and the inner surface of the nano pore canal 4 of the Nafion film has negative charge; and then the two PET nano porous membranes 1 are respectively combined with a Nafion membrane 3, a gate electrode 5 is arranged on the Nafion membrane 3 (nano porous membrane in a gate control area), and a driving electrode adopts an Ag/AgCl electrode to obtain the nano-fluidic field effect transistor with an NPN structure.
The schematic diagram of the current amplifying system of the nanofluidic field effect transistor of the NPN structure is shown as b in fig. 3.
As another preferred embodiment, the nanofluidic field effect tube is composed of a PET nano porous membrane, a polyaniline membrane, an electrode and the like, wherein the size of a nano pore canal of the PET nano porous membrane is 20-50nm, and the inner surface of the nano pore canal of the unmodified PET nano porous membrane is negatively charged; the inner surface of the polyaniline film has positive charges; and then respectively combining the two PET nano porous films and the polyaniline film to form a sandwich structure, wherein a gate electrode is arranged on the polyaniline film, and a driving electrode adopts an Ag/AgCl electrode to obtain the nano-fluidic field effect transistor with the PNP structure. The schematic diagram of the current amplifying system of the nanofluidic field effect transistor with the PNP structure is shown as a in fig. 3.
According to a second aspect of the present invention, there is provided a method for manufacturing a nanofluidic field effect transistor, comprising the steps of:
(a) Providing a PET nano porous membrane, and then modifying the PET nano porous membrane to enable the inner surface of a nano pore canal to have positive charges, or providing a polyaniline membrane;
(b) And (3) coating a layer of Nafion film or unmodified PET nano porous film on the surface of the PET nano porous film or polyaniline film with positive charges on the inner surface of the nano pore canal obtained in the step (a), combining the Nafion film or unmodified PET nano porous film with the positive charges on the inner surface of the nano pore canal obtained in the other step (a), and applying a gate electrode on the Nafion film or unmodified PET nano porous film to obtain the nano-fluidic field effect tube with an NPN structure.
According to a second aspect of the present invention, there is also provided a method for manufacturing a nanofluidic field effect transistor, comprising the steps of:
(a) Providing a PET nano porous membrane, and then modifying the PET nano porous membrane to enable the inner surface of a nano pore canal to have positive charges, or providing a polyaniline membrane;
(b) Providing an unmodified PET nanoporous membrane or Nafion membrane; and (c) superposing a layer of PET nano-porous membrane or a layer of polyaniline membrane with positive charges on the inner surface of the nano-pore canal obtained in the step (a) on the surface of the unmodified PET nano-porous membrane or the Nafion membrane, combining the PET nano-porous membrane or the Nafion membrane with the positive charges with the other unmodified PET nano-porous membrane or the Nafion membrane, and applying a gate electrode on the PET nano-porous membrane or the polyaniline membrane with the positive charges on the inner surface of the nano-pore canal to obtain the nano-fluidic field-effect transistor with the PNP structure.
As a preferred embodiment, the method for constructing the nanofluidic field effect transistor of the NPN structure includes:
controlling the size of a nano pore canal in the PET nano porous membrane to be 20-50nm, and then modifying the PET nano porous membrane to enable the PET nano porous membrane to be positively charged; then coating Nafion solution on the surface of the PET nano porous membrane, volatilizing to form a membrane, combining the membrane with another PET nano porous membrane with positive charges, leading out a wire from the Nafion membrane by adopting conductive silver colloid, constructing a gate potential control device, and constructing the nano-fluidic field effect transistor with an NPN structure through the steps.
As another preferred embodiment, the method for constructing the nanofluidic field effect transistor with the PNP structure includes:
controlling the size of a nano pore canal in the PET nano porous membrane to be 20-50nm, wherein the unmodified PET nano porous membrane has negative charges; and combining the two PET nano porous membranes with negative charges with the polyaniline membrane to construct a sandwich structure. And a conducting silver adhesive is adopted to lead out a conducting wire from the polyaniline film, a gate potential control device is built, and the nano-fluidic field effect transistor with the PNP structure is built through the steps.
According to a third aspect of the invention, there is provided an application of a nanofluidic field effect transistor in biomolecule detection or preparation of an artificial neural network switching device.
The invention can be used for reducing the gate potential<2V) achieves a large current amplification effect with a magnification ratio of 1000 times (ion concentration 10 mM); current detection limit 10×10 -15 A, A is as follows; the amplification efficiency of 830 times is realized at high ionic strength (100 mM), and the method is suitable for biomolecule detection.
The invention can realize the Sigmoid response of the ion current signal and can be used as a switching device of an artificial neural network.
Test example 1 nanofluidic field effect transistor current amplification effect
When the driving potential is ensured to be changed from-1V to 1V, the gate potential is changed to examine the change of the current under the driving potential, and different types of current response signals (linear response, rectifying response, sigmoid response, see fig. 4) are obtained.
And obtaining the ratio of the driving current signal under different gate potentials to the current signal in the gate potential, and obtaining the current amplification efficiency of the nanofluidic field effect transistor.
In order to measure the current amplification effect of the nanofluidic field effect tube under different ion concentrations, when different gate potentials (-2V to 2V) and ion drive currents are examined under the ion concentrations of 10mM and 100mM, the electrodes used for measuring the drive currents are a two-electrode system (Ag/AgCl electrodes), the voltage ranges from 1V to-1V, the voltage change amplitude is 10mV/s, the collected current signals and amplification efficiencies under different gate voltages are shown in figure 5, and the result shows that the nanofluidic field effect tube can realize good current amplification efficiency under low gate potential.
Test example 2 Sigmoid response Signal
Consider the case of a sigmoid response curve change at different gate potentials (fig. 6), the test procedure is as follows:
the constructed nanofluidic field effect transistor is placed in the experimental device of fig. 3, a certain potential is applied to the gate control electrode and the driving electrode respectively by using a double-constant potential meter, and the gate control current and the driving current are observed and recorded, so that the current of the driving current under different driving voltages at a certain gate control potential is obtained.
The result shows that the sigmoid response curve is gradually converted into the rectification curve along with the increase of the gate potential to-0.4V, which proves that the controllable sigmoid response of the nano-fluidic field effect transistor can be realized, and provides technical conditions for the application of the nano-fluidic field effect transistor in an artificial neural network.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (5)

1. A nanofluidic field effect transistor, comprising: a first nanoporous membrane, a second nanoporous membrane, and an electrode; the inner surface of the nano pore canal in the first nano porous membrane is provided with positive charges, and the inner surface of the nano pore canal in the second nano porous membrane is provided with negative charges; the electrodes include a gate electrode and a driving electrode;
the two surfaces of the second nano porous film are respectively combined with the first nano porous film, and the gate electrode is arranged on the second nano porous film to construct a nano-fluidic field effect tube;
the size of the nano pore canal in the first nano porous membrane is 20-50nm; the thickness of the first nano porous film is 10-50 mu m;
the size of the nano pore canal in the second nano porous membrane is 20-50nm; the thickness of the second nano porous film is 10-50 mu m;
the nanometer pore canal in the first nanometer porous membrane is conical;
the first nano porous membrane is a modified PET nano porous membrane or a polyaniline membrane;
the second nano-porous membrane is a Nafion membrane or an unmodified PET nano-porous membrane.
2. The nanofluidic field effect tube according to claim 1, wherein a conducting wire is led out of the second nano-porous membrane by adopting conductive silver paste to form a gate electrode;
the driving electrode adopts an Ag/AgCl electrode.
3. A method for preparing the nanofluidic field effect transistor according to claim 1 or 2, comprising the following steps:
(a) Providing a PET nano porous membrane, and then modifying the PET nano porous membrane to enable the inner surface of a nano pore canal to have positive charges, or providing a polyaniline membrane;
(b) Coating a layer of Nafion film or overlapping a layer of unmodified PET nano porous film on the surface of the PET nano porous film or polyaniline film with positive charges on the inner surface of the nano pore canal obtained in the step (a), combining the Nafion film or the polyaniline film with the positive charges on the inner surface of the nano pore canal obtained in the other step (a), and applying a gate electrode on the Nafion film or the unmodified PET nano porous film to obtain the nanofluidic field effect tube.
4. The method of preparing a nanofluidic field effect transistor according to claim 3, wherein in step (a), the method of modifying in the first nanoporous membrane comprises:
firstly, immersing a first nano porous membrane to be modified in a mixed solution of 1- (3-methylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide sulfonate for 30-60 minutes; then the mixture is washed and then placed in (2-aminoethyl) trimethyl ammonium chloride solution for more than 12 hours.
5. Use of the nanofluidic field effect transistor of claim 1 or 2 in biomolecule detection or in the preparation of an artificial neural network switching device.
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