CN110596222A - Carbon nano tube field effect transistor type sensor and preparation method thereof - Google Patents
Carbon nano tube field effect transistor type sensor and preparation method thereof Download PDFInfo
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Classifications
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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
-
- 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 adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
- H01L29/0657—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body
- H01L29/0665—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body the shape of the body defining a nanostructure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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 System
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
Abstract
The application discloses carbon nanotube field effect transistor type sensor and preparation method thereof, carbon nanotube field effect transistor type sensor has set up one deck and can the homogeneous cover in carbon nanotube layer deviates from substrate one side the ultra-thin dielectric layer on carbon nanotube layer can produce the regulation and control of electrical properties to the carbon nanotube layer as the channel effectively when sensitive layer adsorbs the target substance in the course of the work for the sensitive layer is more global average to the effect of channel, has effectively promoted carbon nanotube field effect transistor type sensor's sensing efficiency, has promoted carbon nanotube field effect transistor type sensor's sensitivity. The existence of the dielectric layer also provides a suspension bond which can be connected by covalent bonds for the modification of the sensitive layer, so that the sensitive layer can be arranged on the dielectric layer in a covalent modification mode, the modification method of the sensitive layer is expanded, and the problem of low yield of the traditional carbon nanotube field effect transistor type sensor is solved.
Description
Technical Field
The application relates to the technical field of semiconductors, in particular to a carbon nanotube field effect transistor type sensor and a preparation method thereof.
Background
The carbon nanotube field effect transistor type sensor can be used as a gas sensor to detect specific gas molecules in a gas or as a biosensor to detect specific biological substances in a sample.
The detection principle of the carbon nanotube field effect transistor type sensor is basically as follows: the sensitive layer which captures the target substance can change the channel conductance of the carbon nano tube nearby the sensitive layer, so that the electrical output parameter of the carbon nano tube field effect transistor is changed, and a detector can judge whether the target substance exists in the sample through whether the electrical output parameter is changed or not, and can even judge the concentration and other parameters of the target substance existing in the sample through the change of the electrical output parameter.
However, in the actual process of sensor preparation and application, it is found that direct surface modification of the carbon nanotubes in the carbon nanotube field effect transistor sensor is very difficult, the success rate of directly forming a sensitive layer on the carbon nanotubes is very low, which results in low yield of the carbon nanotube field effect transistor sensor, and the sensitivity of the carbon nanotube field effect transistor sensor is low because the sensitive layer cannot effectively cover the surface of the carbon nanotubes.
Disclosure of Invention
In order to solve the technical problems, the application provides a carbon nanotube field effect transistor type sensor and a preparation method thereof, so as to solve the problems of low yield and low sensitivity of the carbon nanotube field effect transistor type sensor caused by the difficulty in direct modification on the surface of a carbon nanotube layer in the prior art.
In order to solve the above technical problem, the embodiment of the present application provides the following technical solutions:
a carbon nanotube field effect transistor type sensor comprising:
a substrate;
the carbon nanotube layer, the source electrode and the drain electrode are positioned on one side of the substrate;
the dielectric layer is positioned on the surface of one side, away from the substrate, of the carbon nano tube layer and between the source electrode and the drain electrode;
the sensitive layer is positioned on one side of the dielectric layer, which is far away from the carbon nano tube layer;
the first passivation layer covers the surface of one side, away from the substrate, of the source electrode and the surface of the side wall, facing the dielectric layer, of the source electrode;
and the second passivation layer covers the surface of one side of the drain electrode, which is far away from the substrate, and the surface of the side wall of the drain electrode, which is towards the dielectric layer.
Optionally, the dielectric layer is a high-k dielectric layer.
Optionally, the high-k dielectric layer is an yttrium oxide thin film layer or a hafnium oxide thin film layer or an aluminum oxide thin film dielectric layer.
Optionally, the source electrode and the drain electrode both cover a part of the surface of the carbon nanotube layer on the side away from the substrate;
the source electrode is positioned on one side of the carbon nano tube layer in the first direction and also covers the surface of the side wall of the carbon nano tube layer on one side in the first direction;
the drain electrode is located on one side of the second direction of the carbon nano tube layer and also covers the surface of the side wall on one side of the second direction of the carbon nano tube layer, and the directions of the first direction and the second direction are opposite.
Optionally, the carbon nanotube layer is a network-shaped semiconductor-type carbon nanotube film or an arrayed semiconductor-type carbon nanotube film.
A carbon nanotube field effect transistor type sensor comprising:
a substrate;
the carbon nanotube layer, the source electrode and the drain electrode are positioned on one side of the substrate;
the modification regions are positioned on the surface of the substrate and positioned on two sides of the carbon nanotube layer respectively;
a sensitive layer located on the modified region.
Optionally, the sensitive layer includes:
a silane coupling agent layer located on the surface of the modification region of the substrate;
a functional group on a side of the silane coupling agent layer facing away from the substrate;
and a detecting group which is located on the side of the functional group away from the silane coupling agent layer and is in covalent bond connection with the functional group.
A method for preparing a carbon nanotube field effect transistor type sensor comprises the following steps:
providing a substrate;
preparing and forming a carbon nanotube layer, a source electrode and a drain electrode on the substrate;
forming a mask layer on the substrate, wherein the mask layer at least exposes modification regions which are positioned on the surface of the substrate and are respectively positioned on two sides of the carbon nano tube layer;
and forming a sensitive layer on the modified region.
Optionally, the forming a mask layer on the substrate includes:
spin-coating an electron beam glue layer on the substrate;
forming a hollow window in the electron beam adhesive layer by using an electron beam exposure method so as to enable the electron beam adhesive layer to be the mask layer, wherein the hollow window exposes the modification region and the carbon nano tube layer between the modification regions;
or comprises the following steps:
spin-coating an electron beam glue layer on the substrate;
and applying a first voltage to the carbon nano tube layer, applying a second voltage to the source electrode and the drain electrode to form a hollow window in the electron beam adhesive layer, so that the electron beam adhesive layer becomes the mask layer, and the hollow window exposes the modification region and the carbon nano tube layer between the modification regions.
It can be seen from the foregoing technical solutions that, the present application provides a carbon nanotube field effect transistor sensor and a method for manufacturing the same, and through research, the inventors found that, since a carbon nanotube in a carbon nanotube layer is a tubular structure substance formed by hybridization of carbon atoms with SP2, the surface of the carbon nanotube layer only has in-plane delocalized large pi bonds, and the surface lacks out-of-plane dangling bonds, and direct modification of the carbon nanotube cannot be achieved through a conventional covalent modification manner, therefore, the carbon nanotube field effect transistor sensor provided in the present application provides a dielectric layer that can uniformly cover the carbon nanotube layer on a side of the carbon nanotube layer away from a substrate, and when a sensitive layer adsorbs a target substance in a working process, the sensitive layer can effectively generate control of electrical properties on the carbon nanotube layer serving as a channel, so that the effect of the sensitive layer on the channel is more globally average, the sensing efficiency of the carbon nano tube field effect transistor type sensor is effectively improved, and the sensitivity of the carbon nano tube field effect transistor type sensor is improved. The existence of the dielectric layer also provides a suspension bond which can be connected by covalent bonds for the modification of the sensitive layer, so that the sensitive layer can be arranged on the dielectric layer in a covalent modification mode, the modification method of the sensitive layer is expanded, and the problem of low yield of the traditional carbon nanotube field effect transistor type sensor is solved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a carbon nanotube field effect transistor sensor according to an embodiment of the present application;
FIG. 2 is a schematic diagram showing the current variation with time when the carbon nanotube field effect transistor sensor with the dielectric layer and the conventional carbon nanotube field effect transistor sensor are used as gas sensors according to the embodiment of the present application;
fig. 3 is a comparison of response between a carbon nanotube field effect transistor sensor with a dielectric layer and a conventional carbon nanotube field effect transistor sensor as a gas sensor according to an embodiment of the present disclosure;
FIG. 4 is a graph showing the magnitude of current response to a target substance when a conventional carbon nanotube FET sensor is used as a biosensor;
fig. 5 is a graph showing the response of the carbon nanotube field effect transistor sensor as a biosensor to a target substance according to an embodiment of the present disclosure;
FIG. 6 is a schematic structural diagram of a carbon nanotube field effect transistor sensor according to an embodiment of the present application;
FIG. 7 is a schematic cross-sectional view taken along line GG' of FIG. 6;
fig. 8 is a schematic flow chart of a method for manufacturing a carbon nanotube field effect transistor sensor according to an embodiment of the present application.
Detailed Description
As described in the background art, the size of carbon nanotubes is 1-2nm, which is easily controlled by external molecules and thus is very suitable for use as biosensors. However, in the prior art, the direct surface modification of the sensitive layer of the carbon nanotube field effect transistor sensor on the carbon nanotube layer is very difficult because the carbon nanotubes in the carbon nanotube layer are tubular structural substances formed by hybridization of carbon atoms with SP2, the surface of the carbon nanotubes only has large pi bonds in-plane delocalization, and the surface lacks of dangling bonds out of plane, so that the sensitive layer cannot be stably formed on the carbon nanotube layer in a covalent modification manner through the dangling bonds.
It is studied to produce dangling bonds by destroying defects of carbon nanotubes, so that covalent modification of a sensitive layer on the carbon nanotubes can be realized through the dangling bonds, or covalent modification of the sensitive layer on the carbon nanotubes can be realized through pi-pi bond stacking or modification by using metal as a medium, but the methods have the problems of destroying the properties of the carbon nanotubes, extremely low modification efficiency and unstable modification molecules, so that the performance loss of the carbon nanotube field effect transistor type sensor is caused, and the stability of the carbon nanotube field effect transistor type sensor is reduced.
In view of the above, an embodiment of the present application provides a carbon nanotube field effect transistor type sensor, including:
a substrate;
the carbon nanotube layer, the source electrode and the drain electrode are positioned on one side of the substrate;
the dielectric layer is positioned on the surface of one side, away from the substrate, of the carbon nano tube layer and between the source electrode and the drain electrode;
the sensitive layer is positioned on one side of the dielectric layer, which is far away from the carbon nano tube layer;
the first passivation layer covers the surface of one side, away from the substrate, of the source electrode and the surface of the side wall, facing the dielectric layer, of the source electrode;
and the second passivation layer covers the surface of one side of the drain electrode, which is far away from the substrate, and the surface of the side wall of the drain electrode, which is towards the dielectric layer.
The carbon nanotube field effect transistor type sensor that this application embodiment provided has set up one deck and can the homogeneous cover in carbon nanotube layer deviates from substrate one side the dielectric layer on carbon nanotube layer can produce the regulation and control of electrical property to the carbon nanotube layer as the channel effectively when sensitive layer adsorbs the target substance in the course of the work for the sensitive layer is more global average to the effect of channel, has effectively promoted the sensing efficiency of carbon nanotube field effect transistor type sensor, has promoted the sensitivity of carbon nanotube field effect transistor type sensor. The existence of the dielectric layer also provides a suspension bond which can be connected by covalent bonds for the modification of the sensitive layer, so that the sensitive layer can be arranged on the dielectric layer in a covalent modification mode, the modification method of the sensitive layer is expanded, and the problem of low yield of the traditional carbon nanotube field effect transistor type sensor is solved.
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the present application provides a carbon nanotube field effect transistor type sensor, as shown in fig. 1, including:
a substrate 10;
a carbon nanotube layer 20, a source electrode 31 and a drain electrode 32 on one side of the substrate 10;
the dielectric layer 60 is positioned on the surface of one side, away from the substrate 10, of the carbon nanotube layer 20 and between the source electrode 31 and the drain electrode 32;
the sensitive layer 50 is positioned on one side of the dielectric layer 60, which is far away from the carbon nanotube layer 20;
a first passivation layer 41 covering the surface of the source electrode 31 on the side away from the substrate 10 and the surface of the sidewall of the source electrode 31 on the side facing the dielectric layer 60;
and the second passivation layer 42 covers the surface of the side, facing away from the substrate 10, of the drain electrode 32 and the surface of the side wall, facing the dielectric layer 60, of the drain electrode 32.
The inventor discovers through research that, because the carbon nanotubes in the carbon nanotube layer 20 are tubular structural substances formed by hybridization of carbon atoms with SP2, the surface of the carbon nanotubes only has large pi bonds in-plane delocalization, and the surface lacks out-of-plane dangling bonds, and direct modification of the carbon nanotubes cannot be realized through the traditional covalent modification mode, therefore, the carbon nanotube field effect transistor sensor provided by the embodiment of the application is provided with the dielectric layer 60 which can uniformly cover the carbon nanotube layer 20 and has an extremely thin thickness on the side of the carbon nanotube layer 20 away from the substrate 10, and the dielectric layer 60 provides the dangling bonds which can be connected by covalent bonds for the sensitive layer 50, so that the sensitive layer 50 can be arranged on the dielectric layer 60 in the covalent modification mode, and the sensitive layer 50 can effectively generate regulation and control of electrical properties of the carbon nanotube layer 20 as a channel when adsorbing a target substance in a working process, the effect of the sensitive layer 50 on the channel is more global and average, the sensing efficiency of the carbon nanotube field effect transistor type sensor is effectively improved, the sensitivity of the carbon nanotube field effect transistor type sensor is improved, and the problem of low yield of the traditional carbon nanotube field effect transistor type sensor is solved.
Optionally, the dielectric layer 60 is an ultra-thin dielectric layer 60, in this application, the corresponding ultra-thin Thickness is defined as "less than or equal to 10 nm", in an optional embodiment of this application, a value range of the Thickness of the dielectric layer 60 may be 6 to 8nm, a value of an Equivalent Oxide Thickness (EOT) of the dielectric layer 60 is about 2nm, and a specific Thickness value of the dielectric layer 60 is determined according to a type of a material forming the dielectric layer 60.
As can be seen from the above description, the surface of the formed dielectric layer 60 needs to have a dangling bond, and generally needs to have a high dielectric constant and a good interface wettability with the carbon nanotube, so as to enhance the control capability of the gate electrode of the carbon nanotube field effect transistor sensor on the channel, so that the change of the work function effectively changes the channel conductance of the carbon nanotube field effect transistor sensor. In an alternative embodiment of the present application, the dielectric layer 60 is 6nmY2O3A dielectric layer.
In some embodiments of the application, the substrate 10 may be selected to be a silicon substrate 10, a hard substrate 10 such as silicon dioxide, or a flexible substrate 10 formed of a flexible material.
The source electrode 31 and the drain electrode 32 may be formed of a P-type carbon nanotube field effect transistor sensor using a high work function metal such as Palladium (Pd), or may be formed of an N-type carbon nanotube field effect transistor sensor using a low work function metal such as Scandium (Scandium, Sc).
The first passivation layer 41 and the second passivation layer 42 may be various e-beam resists, photoresists, silicon nitride (SiN)x) Or a film layer formed of a dielectric such as silicon oxide. The existence of the first passivation layer 41 and the second passivation layer 42 can play a role in protecting the source electrode 31 and the drain electrode 32, thereby being beneficial to avoiding the electric leakage condition of the carbon nanotube field effect transistor type sensor when working in liquid and being beneficial to improving the field effect transistor type sensorThe stability of the carbon nanotube field effect transistor type sensor.
The carbon nanotube layer 20 may be a network-shaped semiconductor-type carbon nanotube film or an aligned semiconductor-type carbon nanotube film.
In a preferred embodiment of the present application, still referring to fig. 1, the source electrode 31 and the drain electrode 32 both cover a portion of the surface of the carbon nanotube layer 20 on the side facing away from the substrate 10;
the source electrode 31 is located on one side of the carbon nanotube layer 20 in the first direction, and also covers the surface of the sidewall of the carbon nanotube layer 20 on one side in the first direction;
the drain electrode 32 is located on one side of the carbon nanotube layer 20 in the second direction, and also covers the surface of the sidewall of the carbon nanotube layer 20 on one side in the second direction, and the directions of the first direction and the second direction are opposite.
In fig. 1, the direction indicated by the arrow D1 is the first direction, and the direction indicated by the arrow D2 is the second direction. In this embodiment, the source electrode 31 and the drain electrode 32 both cover the sidewall surfaces of the two ends of the carbon nanotube layer 20, and it is found in the practical application process that the carbon nanotube field effect transistor sensor having such a structure has more excellent electrical properties.
In an optional embodiment of the present application, the dielectric layer 60 is a high-k dielectric thin film layer, and optionally, the dielectric layer 60 is an ultra-thin high-k dielectric thin film layer.
Optionally, the high-k dielectric film layer is an yttrium oxide film layer, a hafnium oxide film layer, an aluminum oxide film dielectric layer, or the like.
The preparation process of the inorganic material film layer can be that the simple substance semiconductor film layer is thermally evaporated and then formed in an oxidation mode, or can be formed through an atomic layer deposition, transfer or spin coating process. The present application does not limit this, which is determined by the actual situation.
In order to verify the practical effect of the carbon nanotube field effect transistor sensor provided in the embodiment of the present application, in an embodiment of the present application, a comparison experiment is performed on the carbon nanotube field effect transistor sensor provided in the embodiment of the present application and a conventional carbon nanotube field effect transistor sensor, and the experimental result refers to fig. 2 to fig. 5.
Fig. 2 shows a schematic diagram of current change with time of the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present application and a conventional carbon nanotube field effect transistor sensor as a gas sensor, wherein a curve C shows a schematic diagram of current change with time of the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present application as a gas sensor, a curve D shows a schematic diagram of current change with time of the conventional carbon nanotube field effect transistor sensor as a gas sensor, and an abscissa in fig. 2 is time and an ordinate is Drain 32 current (Drain I); fig. 3 shows a comparison between the Response of the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present application and the Response of the conventional carbon nanotube field effect transistor sensor as a gas sensor, where the ordinate in fig. 3 is the Response (Response) size, the bar denoted by reference sign E represents the Response size of the conventional carbon nanotube field effect transistor sensor as a gas sensor, and the bar denoted by reference sign F represents the Response size of the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present application as a gas sensor.
As can be seen from fig. 2 and 3, compared with the conventional carbon nanotube field effect transistor sensor, the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present invention has a larger response to the target substance when used as a gas sensor, which indicates that the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present invention effectively improves the sensing efficiency and sensitivity.
Fig. 4 shows the magnitude of Current Response (Current Response) for a target substance when a conventional carbon nanotube field effect transistor sensor is used as a biosensor, the abscissa in fig. 4 is the Device (Device) number, and the ordinate is the magnitude of Response (Response); fig. 5 shows the Response magnitude of the carbon nanotube field effect transistor sensor as a biosensor, where the abscissa in fig. 5 is the Device (Device) number and the ordinate is the Response (Response) magnitude. As can be seen from fig. 4 and 5, when the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present application is used as a biosensor, the response to a target substance is larger than that of a conventional carbon nanotube field effect transistor sensor, which means that the carbon nanotube field effect transistor sensor with the dielectric layer 60 provided in the embodiment of the present application effectively improves sensing efficiency and sensitivity.
In summary, the embodiments of the present application provide a carbon nanotube field effect transistor sensor, the carbon nanotube field effect transistor type sensor is provided with a medium layer 60 which can uniformly cover the carbon nanotube layer 20 on the side of the carbon nanotube layer 20 away from the substrate 10, and the dielectric layer 60 provides a dangling bond capable of being connected by a covalent bond for the sensitive layer 50, so that the sensitive layer 50 can be arranged on the dielectric layer 60 by a covalent modification manner, the sensitive layer 50 can effectively regulate and control the electrical property of the carbon nanotube layer 20 as a channel when adsorbing a target substance during the operation, the effect of the sensitive layer 50 on the channel is more global and average, the sensing efficiency of the carbon nano tube field effect transistor type sensor is effectively improved, the sensitivity of the carbon nano tube field effect transistor type sensor is improved, and the problem of low yield of the traditional carbon nanotube field effect transistor type sensor is solved.
Accordingly, in an embodiment of the present application, another possible structure of a carbon nanotube field effect transistor is provided, as shown in fig. 6 and 7, where fig. 7 is a schematic cross-sectional view taken along line GG' of fig. 6, the carbon nanotube field effect transistor includes:
a substrate 100;
a carbon nanotube layer 300, a source electrode 201 and a drain electrode 202 on one side of the substrate 100;
the modification regions 400 are located on the surface of the substrate 100 and located on two sides of the carbon nanotube layer 300 respectively;
a sensitive layer 500 located on the modified region 400.
In some embodiments of the present application, the carbon nanotube field effect transistor further comprises:
a first passivation layer covering the surface of one side of the source electrode 201, which faces away from the substrate 100, and the surface of the side wall of the source electrode 201, which faces the dielectric layer;
and a second passivation layer covering the surface of the drain electrode 202 on the side away from the substrate 100 and the surface of the side wall of the drain electrode 202 on the side facing the dielectric layer.
In this embodiment, the sensitive layer 500 is formed in the modification region 400 on the substrate 100, and the modification region 400 is located on two sides of the carbon nanotube layer 300, so that the sensitive layer 500 can change the channel conductance of the carbon nanotube in the carbon nanotube layer 300 attached thereto due to the static regulation effect, thereby generating a very sensitive sensing effect, facilitating the improvement of the sensing efficiency of the carbon nanotube field effect transistor, improving the sensitivity of the carbon nanotube field effect transistor sensor, and since the modification region 400 is located on the substrate 100 on two sides of the carbon nanotube layer 300, the problem of low yield caused by the difficulty in modifying the carbon nanotube layer 300 in the prior art is solved.
The carbon nanotube field effect transistor provided in the embodiment of the present application generally operates as a biosensor in a solution, but may also operate as a gas sensor under some conditions.
Similarly, in some embodiments of the application, the substrate 100 may be selected from a silicon substrate 100, a hard substrate 100 such as silicon dioxide, a flexible substrate 100 formed of a flexible material, and the like.
The source 201 and the drain 202 may be formed by a P-type carbon nanotube field effect transistor sensor using a high work function metal such as Palladium (Pd), or may be formed by an N-type carbon nanotube field effect transistor sensor using a low work function metal such as Scandium (Sc).
The first and second passivation layers may be various e-beam resists, photoresists, silicon nitride (SiN)x) Or a film layer formed of a dielectric such as silicon oxide. The presence of the first passivation layer and the second passivation layer may serve as a pairThe protective effect of the source 201 and the drain 202 is beneficial to avoiding the electric leakage condition of the carbon nanotube field effect transistor type sensor when the carbon nanotube field effect transistor type sensor works in liquid, and is beneficial to improving the stability of the carbon nanotube field effect transistor type sensor.
The carbon nanotube layer 300 may be a network-shaped semiconductor-type carbon nanotube film or an aligned semiconductor-type carbon nanotube film.
In an alternative embodiment of the present application, a possible sensitive layer 500 configuration is provided, comprising:
a silane coupling agent layer located on the surface of the modification region 400 of the substrate 100;
a functional group on a side of the silane coupling agent layer facing away from the substrate 100;
and a detecting group which is located on the side of the functional group away from the silane coupling agent layer and is in covalent bond connection with the functional group.
The silane coupling agent is used for modifying the surface of the substrate 100, and functional groups such as amino or carboxyl are connected to the other end of the silane coupling agent, so that the functionalization of the surface of the substrate 100 can be realized; the amino or carboxylated surface can be connected with detection groups such as biological protein molecules, DNA molecules and the like through covalent bonds, the protein molecules and the DNA can have charges due to ionization and other effects in a solution, and the channel conductance of the carbon nano tube nearby the protein molecules can be changed due to the electrostatic regulation and control effect, so that a very sensitive sensing effect is generated.
Correspondingly, an embodiment of the present application further provides a method for manufacturing a carbon nanotube field effect transistor-type sensor, as shown in fig. 8, including:
s101: providing a substrate;
s102: preparing and forming a carbon nanotube layer, a source electrode and a drain electrode on the substrate;
s103: forming a mask layer on the substrate, wherein the mask layer at least exposes modification regions which are positioned on the surface of the substrate and are respectively positioned on two sides of the carbon nano tube layer;
s104: and forming a sensitive layer on the modified region.
The mask layer may be a soft mask such as an electron beam resist or a photoresist, or a hard mask such as a semiconductor insulating layer.
The process of forming the mask layer on the substrate may be:
s1031: spin-coating an electron beam glue layer on the substrate;
s1032: and forming a hollow window in the electron beam adhesive layer by using an electron beam exposure method so as to enable the electron beam adhesive layer to be the mask layer, wherein the hollow window exposes the modification region and the carbon nano tube layer between the modification regions.
The electron beam glue layer may be Polymethyl Methacrylate (PMMA).
Steps S1031 and S1032 are one possible method of preparing a mask layer.
In another embodiment of the present application, the process of forming a mask layer on the substrate may be:
s1033: spin-coating an electron beam glue layer on the substrate;
s1034: applying a first voltage to the carbon nanotube layer, applying a second voltage to the source electrode and the drain electrode to form a hollow window in the electron beam adhesive layer, so that the electron beam adhesive layer becomes the mask layer, and the hollow window is exposed out of the modification region and the carbon nanotube layer between the modification regions
In this embodiment, a first voltage is applied to the carbon nanotube layer as a bottom gate voltage to make the carbon nanotube layer in an on state, and then a second voltage is applied to the source and the drain, so that a large current passes through the channel, and the current generates a thermal effect to make the electron beam glue layer on the carbon nanotube flow aside due to the thermal effect, so that a small window spontaneously appears above the carbon nanotube, and the carbon nanotube and the substrate surface near the carbon nanotube are exposed to form a hollow window. The forming area and the size of the hollow window can be finely controlled through adjustment of the first voltage and the second voltage, the minimum control precision can reach several nm, the complex alignment process of electron beam exposure is avoided, the preparation efficiency of the carbon nano tube field effect transistor type sensor is improved, and the preparation cost of the carbon nano tube field effect transistor type sensor is reduced.
To sum up, the embodiment of the application provides a carbon nanotube field effect transistor type sensor and a preparation method thereof, the sensitive layer of the carbon nanotube field effect transistor type sensor is formed in the modification area on the substrate, and the modification area is located on both sides of the carbon nanotube layer, so that the sensitive layer can change the channel conductance of the carbon nanotube in the carbon nanotube layer of the accessory thereof due to the static regulation and control effect, thereby generating a very sensitive sensing effect, being beneficial to promoting the sensing efficiency of the carbon nanotube field effect transistor, improving the sensitivity of the carbon nanotube field effect transistor type sensor, and because the modification area is located on the substrate on both sides of the carbon nanotube layer, and the problem of low yield caused by the great modification difficulty of the carbon nanotube layer in the prior art can not be solved.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A carbon nanotube field effect transistor-type sensor, comprising:
a substrate;
the carbon nanotube layer, the source electrode and the drain electrode are positioned on one side of the substrate;
the dielectric layer is positioned on the surface of one side, away from the substrate, of the carbon nano tube layer and between the source electrode and the drain electrode;
the sensitive layer is positioned on one side of the dielectric layer, which is far away from the carbon nano tube layer;
the first passivation layer covers the surface of one side, away from the substrate, of the source electrode and the surface of the side wall, facing the dielectric layer, of the source electrode;
and the second passivation layer covers the surface of one side of the drain electrode, which is far away from the substrate, and the surface of the side wall of the drain electrode, which is towards the dielectric layer.
2. The carbon nanotube field effect transistor-type sensor according to claim 1, wherein the dielectric layer is a high-k dielectric layer.
3. The carbon nanotube field effect transistor type sensor according to claim 2, wherein the high-k dielectric layer is an yttria thin film layer or a hafnia thin film layer or an alumina thin film dielectric layer.
4. The carbon nanotube field effect transistor type sensor according to claim 1, wherein the source electrode and the drain electrode each cover a portion of a surface of the carbon nanotube layer on a side facing away from the substrate;
the source electrode is positioned on one side of the carbon nano tube layer in the first direction and also covers the surface of the side wall of the carbon nano tube layer on one side in the first direction;
the drain electrode is located on one side of the second direction of the carbon nano tube layer and also covers the surface of the side wall on one side of the second direction of the carbon nano tube layer, and the directions of the first direction and the second direction are opposite.
5. The carbon nanotube field effect transistor type sensor according to claim 1, wherein the carbon nanotube layer is a network-like semiconductor-type carbon nanotube film or an aligned semiconductor-type carbon nanotube film.
6. A carbon nanotube field effect transistor-type sensor, comprising:
a substrate;
the carbon nanotube layer, the source electrode and the drain electrode are positioned on one side of the substrate;
the modification regions are positioned on the surface of the substrate and positioned on two sides of the carbon nanotube layer respectively;
a sensitive layer located on the modified region.
7. The carbon nanotube field effect transistor type sensor according to claim 6, wherein the sensitive layer comprises:
a silane coupling agent layer located on the surface of the modification region of the substrate;
a functional group on a side of the silane coupling agent layer facing away from the substrate;
and a detecting group which is located on the side of the functional group away from the silane coupling agent layer and is in covalent bond connection with the functional group.
8. A method for preparing a carbon nanotube field effect transistor type sensor is characterized by comprising the following steps:
providing a substrate;
preparing and forming a carbon nanotube layer, a source electrode and a drain electrode on the substrate;
forming a mask layer on the substrate, wherein the mask layer at least exposes modification regions which are positioned on the surface of the substrate and are respectively positioned on two sides of the carbon nano tube layer;
and forming a sensitive layer on the modified region.
9. The method of claim 8, wherein forming a mask layer on the substrate comprises:
spin-coating an electron beam glue layer on the substrate;
forming a hollow window in the electron beam adhesive layer by using an electron beam exposure method so as to enable the electron beam adhesive layer to be the mask layer, wherein the hollow window exposes the modification region and the carbon nano tube layer between the modification regions;
or comprises the following steps:
spin-coating an electron beam glue layer on the substrate;
and applying a first voltage to the carbon nano tube layer, applying a second voltage to the source electrode and the drain electrode to form a hollow window in the electron beam adhesive layer, so that the electron beam adhesive layer becomes the mask layer, and the hollow window exposes the modification region and the carbon nano tube layer between the modification regions.
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Application publication date: 20191220 |