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2016-08-02
14/848,267
2015-09-08
US 9,404,880 B1
2016-08-02
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Roy Potter | Paul Patton
Holtz, Holtz & Volek PC
2035-09-08
Smart Summary: A new type of sensor is designed to detect specific substances in liquids. It uses a layer of graphene, which is a special material that changes its electrical properties when certain molecules attach to it. The graphene is shaped like a band and is placed in the path of the liquid flow. Two electrodes are connected to the edges of the graphene band, allowing it to measure changes in electrical signals. This setup aims to improve the sensor's ability to identify target substances with high sensitivity. π TL;DR
The sensor includes a first graphene film that is provided on the insulating layer so as to be located in a flow path of a liquid containing the detection target substance, the first graphene film having a first edge that is parallel with a first direction that is along the flow path and a first edge that is parallel with a second direction that is different from the first direction, and the first graphene film having the shape of a band that extends in the second direction. The sensor includes a first electrode that is electrically connected to the first edge of the first graphene film that is parallel with the first direction. The sensor includes a second electrode that is electrically connected to a second edge of the first graphene film that is opposed to the first edge that is parallel with the first direction.
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G01N27/125 » CPC main
Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid Composition of the body, e.g. the composition of its sensitive layer
H01L29/1606 » CPC further
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; 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 Graphene
H01L29/16 IPC
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; 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
G01N27/12 IPC
Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
This application is based upon and claims the benefit of U.S. provisional Application No. 62/131,770, filed on Mar. 11, 2015, the entire contents of which are incorporated herein by reference.
Embodiments described herein relate generally to a sensor and a method of manufacturing the sensor.
In recent years, there has been a demand for sensitive materials and structures that can be used to provide biosensors.
In particular, use of the graphene film that substantially changes in electrical characteristics in response to adsorption of or coupling with an atom or molecule on the surface has been studied. A conventional biosensor using the graphene film relies on a change in bulk electron conduction characteristics for detection.
However, the electrical characteristics of the graphene film change in response to adsorption of, or other reactions with, most atoms or molecules, so that it is difficult to locate a detection target substance. To overcome this drawback, the biosensor using the graphene film has to have a surface which only the detection target substance is adsorbed to or coupled with.
Thus, it is difficult for the conventional biosensor to detect a target substance with high sensitivity.
FIG. 1 is a diagram for illustrating a molecular structure of graphene;
FIG. 2 is a diagram showing the density of states (DOS) of the graphene;
FIG. 3 is a diagram showing an example of a relationship between the width and the volume resistivity of the graphene film;
FIG. 4 is a diagram showing an example of a state of a graphene film to which a detection target substance βXβ has been adsorbed;
FIG. 5 is a diagram showing a configuration of the biosensor according to the first embodiment;
FIG. 6 is a diagram showing an example of step of the method of manufacturing the biosensor according to the first embodiment;
FIG. 7 is a diagram showing an example of step of the method of manufacturing the biosensor according to the first embodiment, and continuous from FIG. 6;
FIG. 8 is a diagram showing an example of step of the method of manufacturing the biosensor according to the first embodiment, and continuous from FIG. 7;
FIG. 9 is a diagram showing an example of step of the method of manufacturing the biosensor according to the first embodiment, and continuous from FIG. 8;
FIG. 10 is a diagram showing an example of step of the method of manufacturing the biosensor according to the first embodiment, and continuous from FIG. 9;
FIG. 11 is a diagram showing an example of step of the method of manufacturing the biosensor according to the first embodiment, and continuous from FIG. 10;
FIG. 12 is a diagram showing an example of step of a method of manufacturing the biosensor according to the second embodiment, and continuous from FIG. 8;
FIG. 13 is a diagram showing an example of step of a method of manufacturing the biosensor according to the second embodiment, and continuous from FIG. 12;
FIG. 14 is a diagram showing an example of step of a method of manufacturing the biosensor according to the second embodiment, and continuous from FIG. 13; and
FIG. 15 is a diagram showing a configuration of a biosensor according to a third embodiment.
A sensor that detects a detection target substance according to an embodiment includes an insulating layer. The sensor includes a first graphene film that is provided on the insulating layer so as to be located in a flow path of a liquid containing the detection target substance, the first graphene film having a first edge that is parallel with a first direction that is along the flow path and a first edge that is parallel with a second direction that is different from the first direction, and the first graphene film having the shape of a band that extends in the second direction. The sensor includes a first electrode that is electrically connected to the first edge of the first graphene film that is parallel with the first direction. The sensor includes a second electrode that is electrically connected to a second edge of the first graphene film that is opposed to the first edge that is parallel with the first direction.
As described above, a conventional biosensor using a graphene film relies on a change of bulk electron conduction characteristics for detection. The graphene film exhibits edge state-induced electron conduction characteristics if the graphene film has a line shape as the width of the graphene film decreases.
FIG. 1 is a diagram for illustrating a molecular structure of graphene. (A) of FIG. 1 is a diagram showing an example of a molecular structure model of graphene. (B) of FIG. 1 is an enlarged view showing an example (zigzag edge) of a configuration of an edge region βXβ of the graphene shown in (A) of FIG. 1. (C) of FIG. 1 is an enlarged view showing another example (armchair edge) of the configuration of the edge region βXβ of the graphene shown in (A) of FIG. 1. FIG. 2 is a diagram showing the density of states (DOS) of the graphene. (A) of FIG. 2 is showing an example of the DOS of the zigzag edge of the graphene film. (B) of FIG. 2 is showing an example of the DOS of the armchair edge of the graphene film. In (A) and (B) of FIG. 2, the vertical axis indicates energy (E), and the horizontal axis indicates k-point (an arbitrary point having a symmetry in a reciprocal lattice in the crystal). That is, (A) and (B) of FIG. 2 show energy a carrier can have in a direction (at a k-point) in a crystal.
As shown in FIG. 1, the graphene film has a zigzag edge or an armchair edge. As shown in (A) and (B) of FIG. 2, the zigzag edge and the armchair edge have different DOSs.
FIG. 3 is a diagram showing an example of a relationship between the width and the volume resistivity of the graphene film.
As shown in FIG. 3, when the width (line width) of the graphene film becomes equal to or smaller than 100 nm, the edge state-induced characteristics is considered to become remarkable. On the other hand, when the width (line width) of the graphene film becomes equal to or greater than 1 ΞΌm, the bulk conduction-induced characteristics is considered to become remarkable.
FIG. 4 is a diagram showing an example of a state of a graphene film to which a detection target substance βXβ has been adsorbed. The graphene film shown in FIG. 4 has armchair edges at the opposite ends in the first direction βAβ of the flow path of the detection target substance. The graphene film has four or three six-membered rings of carbon atoms arranged in the first direction βAβ (that is, N (=9) carbon atoms are coupled in the first direction βAβ). Furthermore, in the example shown in FIG. 4, the detection target substance is adsorbed to the first (N=1) carbon atom from one edge. The βadsorptionβ of the detection target substance to the carbon atom used herein also means that the detection target substance comes into contact with the carbon atom, that the detection target substance replaces the carbon atom, or that the detection target substance is in contact with the carbon atom via some other substance.
The resistance of the graphene film having the armchair edge decreases (AGNR), while the resistance of the graphene film having the zigzag edge increases (ZGNR). If the detection target substance is adsorbed to the graphene film having the armchair edge, the resistance and the DOS are considered to change in accordance with the composition of the detection target substance.
The edge state-induced electron conduction characteristics change with the width of the graphene film.
As described above, as the width of the graphene film decreases, the graphene film exhibits edge state-induced electron conduction characteristics. The edge state-induced electron conduction characteristics are sensitively modulated in response to adsorption of or reaction with a foreign matter. Furthermore, the extent of the modulation varies with the width of the graphene film.
Therefore, a plurality of detection target substances can be detected at the same time with high sensitivity by monitoring the extent of the modulation of the edge state-induced electron conduction characteristics of graphene films of different line widths.
Thus, according to embodiments, graphene is used in a detecting part for a detection target substance. In particular, according to the embodiments, biosensors are proposed that use a plurality of graphene films of different small widths and can detect a plurality of detection target substances at the same time or can detect a detection target substance with higher sensitivity.
In the following, embodiments will be described with reference to the drawings.
First, a configuration of a biosensor according to a first embodiment will be described.
The biosensor according to this embodiment is to detect a detection target substance, such as an ion, an enzyme, a DNA, an antigen or antibody, or a protein. That is, the biosensor serves as an ion sensor, an enzyme sensor, a DNA sensor, an antigen or antibody sensor, or a protein sensor.
FIG. 5 is a diagram showing a configuration of the biosensor according to the first embodiment. (A) of FIG. 5 is a cross-sectional view of the biosensor taken along a plane βZ1β perpendicular to a first direction βAβ of a flow path of a detection target substance of the biosensor. (B) of FIG. 5 is a cross-sectional view of the biosensor taken along the first direction βAβ of the flow path of the detection target substance of the biosensor. (C) of FIG. 5 is a cross-sectional view of the biosensor taken along a plane βZ2β perpendicular to the first direction βAβ of the flow path of the detection target substance of the biosensor. (D) of FIG. 5 is a top view of the biosensor. In (D) of FIG. 5, illustration of a first side wall insulating layer βW1β, a second side wall insulating layer βW2β and an upper insulating layer βW3β is omitted.
As shown in FIG. 5, the biosensor includes a substrate βSβ, an insulating layer βInβ, a first graphene film βG1β, a second graphene film βG2β, a third graphene film βG3β, a fourth graphene film βG4β, a first electrode βD1β, a second electrode βD2β, a third electrode βD3β, a fourth electrode βD4β, a fifth electrode βD5β, a sixth electrode βD6β, the first side wall insulating layer βW1β, the second side wall insulating layer βW2β, and the upper insulating layer βW3β, for example.
The substrate βSβ is a silicon substrate, for example. The substrate βSβ may be made of a silicon oxide or a polymer material. The flow path through which the detection target substance to be detected by the biosensor or a medium containing the detection target substance flows is located on the substrate βSβ.
The insulating layer βInβ is provided on the substrate βSβ. The insulating layer βInβ is a silicon oxide film. The insulating layer βInβ is intended to prevent discharge. The insulating layer βInβ may be incorporated in the substrate βSβ.
The first graphene film βG1β is provided on the insulating layer βInβ so as to be located in the flow path of the detection target substance (liquid (medium) containing the detection target substance). The first graphene film βG1β has an edge that is parallel with the first direction βAβ, an edge opposed to the edge that is parallel with the first direction βAβ, an edge that is parallel with a second direction βBβ, and an edge opposed to the edge that is parallel with the second direction βBβ. For example, the edge that is parallel with the first direction βAβ and the edge opposed thereto are parallel with each other, and the edge that is parallel with the second direction βBβ and the edge opposed thereto are parallel with each other. That is, the first graphene film βG1β has a substantially rectangular shape that has edges that are parallel with the first direction βAβ and edges that are parallel with the second direction βBβ, the shape being a band-like shape that extends in the second direction βBβ, which is different from the first direction βAβ that is along the flow path. The first direction βAβ and the second direction βBβ are perpendicular to each other in a plane parallel with an upper surface of the substrate βSβ. In the example shown in FIG. 5, the direction of the flow of the detection target substance corresponds to the direction of the arrow of the first direction βAβ along the flow path.
The length of the edge of the first graphene film βG1β that is parallel with the first direction βAβ, that is, the width in the first direction βAβ, is equal to or smaller than a first prescribed value (100 nm in this example) previously set. The first graphene film βG1β contains at least one six-membered ring of carbon atoms in the first direction βAβ.
That is, the bulk conduction-induced characteristics of the first graphene film βG1β is reduced, and the first graphene film βG1β exhibits edge state-induced electron conduction characteristics.
The third graphene film βG3β is provided on the insulating layer βInβ so as to be located in the flow path. The third graphene film βG3β has an edge that is parallel with the first direction βAβ, an edge opposed to the edge that is parallel with the first direction βAβ, an edge that is parallel with the second direction βBβ, and an edge opposed to the edge that is parallel with the second direction βBβ. For example, the edge that is parallel with the first direction βAβ and the edge opposed thereto are parallel with each other, and the edge that is parallel with the second direction βBβ and the edge opposed thereto are parallel with each other. That is, the third graphene film βG3β has a substantially rectangular shape that has edges that are parallel with the first direction βAβ and edges that are parallel with the second direction βBβ, for example, the shape being a band-like shape that extends in the second direction βBβ.
The length of the edge of the third graphene film βG3β that is parallel with the first direction βAβ, that is, the width in the first direction βAβ, is equal to or smaller than the first prescribed value. In the example shown in FIG. 5, the width of the third graphene layer βG3β in the first direction βAβ is set to be equal to the width of the first graphene layer βG1.β in the first direction βAβ. The third graphene film βG3β contains at least one six-membered ring of carbon atoms in the first direction βAβ.
That is, the bulk conduction-induced characteristics of the third graphene film βG3β is reduced, and the third graphene film βG3β exhibits edge state-induced electron conduction characteristics.
The first electrode βD1.β is electrically connected to the edge of the first graphene film βG1.β that is parallel with the first direction βAβ. Furthermore, the first electrode βD1β is electrically connected to the edge of the third graphene film βG3β that is parallel with the first direction βAβ. In the example shown in FIG. 5, the first electrode βD1β is provided on the insulating layer βInβ and the edges of the first and third graphene films βG1β and βG3β that are parallel with the first direction βAβ.
The second electrode βD2β is electrically connected to the edge of the first graphene film βG1β that is opposed to the edge that is parallel with the first direction βAβ. Furthermore, the second electrode βD2β is electrically connected to the edge of the third graphene film βG3β that is opposed to the edge that is parallel with the first direction βAβ. In the example shown in FIG. 5, the second electrode βD2β is provided on the insulating layer βInβ and the edges of the first and third graphene films βG1β and βG3β that are opposed to the edges that are parallel with the first direction βAβ.
As described above, the first and third graphene films βG1β and βG3β are electrically connected in parallel with each other between the first electrode βD1β and the second electrode βD2β. In other words, the first and second electrodes βD1β and βD2β transmit signals for the first and third graphene films βG1β and βG3β.
The edges of the first and third graphene films βG1β and βG3β that are parallel with the second direction βBβ are zigzag edges or armchair edges.
The second graphene film βG2β is provided on the insulating layer βInβ so as to be located in the flow path. The second graphene film βG2β has an edge that is parallel with the first direction βAβ, an edge opposed to the edge that is parallel with the first direction βAβ, an edge that is parallel with the second direction βBβ, and an edge opposed to the edge that is parallel with the second direction βBβ. For example, the edge that is parallel with the first direction βAβ and the edge opposed thereto are parallel with each other, and the edge that is parallel with the second direction βBβ and the edge opposed thereto are parallel with each other. That is, the second graphene film βG2β has a substantially rectangular shape that has edges that are parallel with the first direction βAβ and edges that are parallel with the second direction βBβ, for example, the shape being a band-like shape that extends in the second direction βBβ.
The third electrode βD3β is electrically connected to the edge of the second graphene film βG2β that is parallel with the first direction βAβ. In the example shown in FIG. 5, the third electrode βD3β is provided on the insulating layer βInβ and the edge of the second graphene film βG2β that is parallel with the first direction βAβ.
The fourth electrode βD4β is electrically connected to the edge of the second graphene film βG2β that is opposed to the edge that is parallel with the first direction βAβ. In the example shown in FIG. 5, the fourth electrode βD4β is provided on the insulating layer βInβ and the edge of the second graphene film βG2β that is opposed to the edge that is parallel with the first direction βAβ.
As described above, the second graphene film βG2β is electrically connected between the third electrode βD3β and the fourth electrode βD4β. In other words, the third and fourth electrodes βD3β and βD4β transmit a signal for the second graphene film βG2β.
The length of the edge of the second graphene film βG2β that is parallel with the first direction βAβ, that is, the width in the first direction βAβ, is equal to or smaller than the first prescribed value. That is, the bulk conduction-induced characteristics of the second graphene film βG2β is reduced, and the second graphene film βG2β exhibits edge state-induced electron conduction characteristics.
The width of the second graphene film βG2β differs from the width of the first graphene film βG1.β in the first direction βAβ. In the example shown in FIG. 5, the width of the second graphene film βG2β in the first direction βAβ is equal to or smaller than the first prescribed value and is greater than the width of the first graphene film βG1β in the first direction βAβ. The second graphene film βG2β contains at least one six-membered ring of carbon atoms in the first direction βAβ.
Thus, the second graphene film βG2β exhibits edge state-induced electron conduction characteristics that differ from those of the first and third graphene films βG1.β and βG3β.
The fourth graphene film βG4β is provided on the insulating layer βInβ so as to be located in the flow path. The fourth graphene film βG4β has an edge that is parallel with the first direction βAβ, an edge opposed to the edge that is parallel with the first direction βAβ, an edge that is parallel with the second direction βBβ, and an edge opposed to the edge that is parallel with the second direction βBβ. For example, the edge that is parallel with the first direction βAβ and the edge opposed thereto are parallel with each other, and the edge that is parallel with the second direction βBβ and the edge opposed thereto are parallel with each other. That is, the fourth graphene film βG4β has a substantially rectangular shape that has edges that are parallel with the first direction βAβ and edges that are parallel with the second direction βBβ, for example, the shape being a band-like shape that extends in the second direction βBβ.
The length of the edge of the fourth graphene film βG4β that is parallel with the first direction βAβ, that is, the width in the first direction βAβ, is equal to or greater than a second prescribed value (1 ΞΌm, for example) that is greater than the first prescribed value (100 nm) previously set.
As a result, the fourth graphene film βG4β exhibits bulk conduction-induced characteristics.
The fifth electrode βD5β is electrically connected to the edge of the fourth graphene film βG4β that is parallel with the first direction βAβ. In the example shown in FIG. 5, the fifth electrode βD5β is provided on the insulating layer βInβ and the edge of the fourth graphene film βG4β that is parallel with the first direction βAβ.
The sixth electrode βD6β is electrically connected to the edge of the fourth graphene film βG4β that is opposed to the edge that is parallel with the first direction βAβ. In the example shown in FIG. 5, the sixth electrode βD6β is provided on the insulating layer βInβ and the edge of the fourth graphene film βG4β that is opposed to the edge that is parallel with the first direction βAβ.
As described above, the fourth graphene film βG4β is electrically connected between the fifth electrode βD5β and the sixth electrode βD6β. In other words, the fifth and sixth electrodes βD5β and βD6β transmit a signal for the fourth graphene film βG4β.
The edges of the first to fourth graphene films βG1β to βG4β that are parallel with the second direction βBβ are zigzag edges or armchair edges.
Although the first to fourth graphene films βG1β to βG4β have been described as having a substantially rectangular shape as an example, the first to fourth graphene films βG1β to βG4β may have the shape of a parallelogram or trapezoid, for example.
The first to sixth electrodes βD1β to βD6β contains any of Al, Cu, W and Ni.
A catalyst (not shown), a backing film (not shown) or the like for formation of the graphene films may be provided between the first to fourth graphene films βG1β to βG4β and the insulating layer βInβ.
The first side wall insulating layer βW1β is provided on the insulating layer βInβ along the first direction βAβ on the right side of the flow path. The second side wall insulating layer βW2β is provided on the insulating layer βInβ along the first direction βAβ on the left side of the flow path. The upper insulating layer βW3β is provided above the flow path along the first direction βAβ and is connected to upper parts of the first and second side wall insulating layers βW1β and βW2β.
The first side wall insulating layer βW1β, the second side wall insulating layer βW2β and the upper insulating layer βW3β are made of an insulating material, such as SiO2, SiN or a polymer material. The first side wall insulating layer βW1β, the second side wall insulating layer βW2β and the upper insulating layer βW3β may be integrally formed.
Suppose that a detection target substance is flowed into the flow path of the biosensor in the first direction βAβ, for example. Then, the detection target substance is adsorbed to a carbon atom of each of the first to fourth graphene films βG1β to βG4β. As described above, the βadsorptionβ of the detection target substance to the carbon atom also means that the detection target substance comes into contact with the carbon atom, that the detection target substance replaces the carbon atom, or that the detection target substance is in contact with the carbon atom via some other substance.
The resistances between the first electrode βD1β and the second electrode βD2β, between the third electrode βD3β and the fourth electrode βD4β and between the fifth electrode βD5β and the sixth electrode βD6β are measured. The composition of the detection target substance can be determined from the resistances, the characteristics shown in FIG. 8 and the like. The detection of the detection target substance can rely on the extent to which an electrical characteristic (resistance, for example) increases or decreases. However, the detection of the detection target substance does not have to rely only on the extent to which an electrical characteristic increases or decreases.
For example, graphene films of line widths smaller than the size of the detection target substance can be formed with a high density over a wide area by using a semiconductor manufacturing technique. In that case, if each graphene film is connected to a separate electrode and individually monitored, the size of the detection target substance can be measured.
That is, the biosensor according to this embodiment can also individually evaluate more detection target substances, including determining the relative amounts of the detection target substances.
Next, an example of a method of manufacturing the biosensor configured as described above will be described. FIGS. 6 to 11 are diagrams examples of steps of the method of manufacturing the biosensor according to the first embodiment. (A) of FIGS. 6 to 11 are cross-sectional views taken along the plane βZ1β perpendicular to the first direction βAβ of the flow path of the detection target substance. (B) of FIGS. 6 to 11 are cross-sectional views taken along the first direction βAβ of the flow path of the detection target substance.
First, as shown in FIG. 6, the insulating layer βInβ is formed on the substrate βSβ.
As shown in FIG. 7, a graphene film βGβ is then formed on the insulating layer βInβ by chemical vapor deposition (CVD), for example.
The graphene film βGβ may be formed by graphite transfer. When the graphite transfer process is used, graphene patterned by a printing technique may be applied, for example.
As shown in FIG. 8, the graphene film βGβ is patterned by lithography, for example. In this step, in the case where only changes in edge state-induced characteristics are to be monitored, a hard mask used in the patterning (not shown) or the like may be left on the graphene film.
In this way, the first to fourth graphene films βG1β to βG4β having the shape of a band that extends in the second direction βBβ are formed on the insulating layer βInβ so as to be located in the flow path.
As an alternative, a backing material (not shown) for formation of the graphene film may be patterned in advance, and the first to fourth graphene films βG1β to βG4β may then be selectively formed by CVD or the like.
In this way, the first to third graphene films βG1β to βG3β that have a width in the first direction βAβ that is equal to or smaller than the first prescribed value (100 nm, in this example), for which an edge state-induced electron state is dominant, and the fourth graphene film βG4β that has a width in the first direction βAβ that is equal to or greater than the second prescribed value (1 for example), which exhibits bulk electron conduction characteristics, are formed.
As shown in FIG. 9, the first, third and fifth electrodes βD1β, βD3β and βD5β electrically connected to the edges of the first to fourth graphene films βG1β to βG4β that are parallel with the first direction βAβ and the second, fourth and sixth electrodes βD2β, βD4β and βD6β electrically connected to the edges of the first to fourth graphene films βG1β to βG4β that are opposed to the edges that are parallel with the first direction βAβ are formed.
As described above, the first to sixth electrodes βD1β to βD6β are made of a material containing any of Al, Cu, W and Ni.
An insulating layer of SiO2 or the like is deposited on a substrate (not shown) that can be lifted off, the insulating layer is patterned, and the patterned insulating layer is lifted off, for example. In this way, as shown in FIG. 10, the first side wall insulating layer βW1β, the second side wall insulating layer βW2β, and the upper insulating layer βW3β connected to the upper parts of the first and second side wall insulating layers βW1β and βW2β are formed.
As shown in FIG. 11, the substrate βSβ with the first to fourth graphene films βG1β to βG4β formed thereon as shown in FIG. 9 and the structure of the first side wall insulating layer βW1β, the second side wall insulating layer βW2β and the upper insulating layer βW3β formed in the step shown in FIG. 10 is then bonded to each other so as to form the flow path.
In this way, the first side wall insulating layer βW1β extending in the first direction βAβ on the right side of the flow path on the insulating layer βInβ, the second side wall insulating layer βW2β extending in the first direction βAβ on the left side of the flow path on the insulating layer βInβ, and the upper insulating layer βW3β connected to the upper parts of the first and second side wall insulating layers βW1β and βW2β and extending in the first direction βAβ above the flow path are formed.
In the process described above, the biosensor shown in FIG. 5 is completed.
As described above, the biosensor according to this embodiment can detect a detection target substance with high sensitivity.
A second embodiment described below concerns another example of the method of manufacturing the biosensor.
FIGS. 12 to 14 are diagrams showing examples of steps of a method of manufacturing the biosensor according to the second embodiment. (A) of FIG. 12 to (A) FIG. 14 are cross-sectional views taken along the plane βZ1β perpendicular to the first direction βAβ of the flow path of the detection target substance. (B) of FIG. 12 to (B) of FIG. 14 are cross-sectional views taken along the first direction βAβ of the flow path of the detection target substance. The method of manufacturing the biosensor according to the second embodiment is the same as the method according to the first embodiment until the step shown in FIG. 9.
As described above with regard to the first embodiment, the first, third and fifth electrodes βD1β, βD3β and βD5β electrically connected to the edges of the first to fourth graphene films βG1β to βG4β that are parallel with the first direction βAβ and the second, fourth and sixth electrodes βD2β, βD4β and βD6β electrically connected to the edges of the first to fourth graphene films βG1β to βG4β that are opposed to the edges that are parallel with the first direction βAβ are formed (FIG. 9).
As shown in FIG. 12, a sacrificial layer 20 of SiN or the like is then formed on the insulating layer βInβ and the first to fourth graphene films βG1β to βG4β at a position where the flow path is to be formed.
As shown in FIG. 13, an insulating layer of a material such as SiO2 is then formed on the substrate βSβ, thereby forming the first side wall insulating layer βW1β extending in the first direction βAβ on the right side of the flow path on the insulating layer βInβ, the second side wall insulating layer βW2β extending in the first direction βAβ on the left side of the flow path on the insulating layer βInβ, and the upper insulating layer βW3β connected to the upper parts of the first and second side wall insulating layers βW1β and βW2β and extending in the first direction βAβ above the flow path.
As shown in FIG. 14, the sacrificial layer 20 is selectively removed by wet etching using an etchant such as phosphoric acid, thereby forming the flow path.
In the process described above, the biosensor according to the second embodiment is completed.
In other respects, the configuration of the biosensor formed in the manufacturing method and the method of manufacturing the biosensor are the same as those according to the first embodiment.
The remainder of the characteristics of the operation of the biosensor is the same as that in the first embodiment.
As described above, the biosensor according to this embodiment can detect a detection target substance with high sensitivity.
If the width of the graphene film is not sufficiently small, the bulk conduction-induced characteristics can be detected along with the edge state-induced characteristics in detection of the detection target substance. To reduce the bulk conduction-induced characteristics, a protective film can be formed on the graphene film in such a manner that edges of the graphene film are exposed. Such a structure will now be described.
FIG. 15 is a diagram showing a configuration of a biosensor according to a third embodiment. (A) of FIG. 15 is a cross-sectional view of the biosensor taken along the plane βZ1β perpendicular to the first direction βAβ of the flow path of the detection target substance of the biosensor. (B) of FIG. 15 is a cross-sectional view of the biosensor taken along the first direction βAβ of the flow path of the detection target substance of the biosensor. (C) of FIG. 15 is a cross-sectional view of the biosensor taken along the plane βZ2β perpendicular to the first direction βAβ of the flow path of the detection target substance of the biosensor. (D) of FIG. 15 is a top view of the biosensor. In (D) of FIG. 15, illustration of the first side wall insulating layer βW1β, the second side wall insulating layer βW2β and the upper insulating layer βW3β is omitted. In FIG. 15, the same reference symbols as those in FIG. 5 denote the same components as those in the first embodiment, and description of the components will be omitted.
As shown in FIG. 15, the biosensor includes the substrate βSβ, the insulating layer βInβ, the first graphene film βG1β, the second graphene film βG2β, the third graphene film βG3β, the fourth graphene film βG4β, the first electrode βD1β, the second electrode βD2β, the third electrode βD3β, the fourth electrode βD4β, the fifth electrode βD5β, the sixth electrode βD6β, the first side wall insulating layer βW1β, the second wide wall insulating layer βW2β, the upper insulating layer βW3β, and protective films βT1β, βT2β, and βT3β, for example.
That is, the biosensor according to this embodiment differs from the biosensor according to the first embodiment in that the biosensor further includes the protective films βT1β, βT2β and βT3β.
The protective film βT1β is provided on the first graphene film βG1β in such a manner that the edge of the first graphene film βG1β that is parallel with the second direction βBβ and the edge of the first graphene film βG1β that is opposed to the edge that is parallel with the second direction βBβ are exposed.
The protective film βT1β prevents the detection target substance or the liquid containing the detection target substance from coming into contact with the part of the surface of the first graphene film βG1β that is covered with the protective film βT1β.
As a result, the bulk conduction-induced characteristics of the first graphene film βG1β can be reduced, and the edge state-induced characteristics can be made more detectable.
The protective film βT2β is provided on the second graphene film βG2β in such a manner that the edge of the second graphene film βG2β that is parallel with the second direction βBβ and the edge of the second graphene film βG2β that is opposed to the edge that is parallel with the second direction βBβ are exposed.
The protective film βT2β prevents the detection target substance or the liquid containing the detection target substance from coming into contact with the part of the surface of the second graphene film βG2β that is covered with the protective film βT2β.
As a result, the bulk conduction-induced characteristics of the second graphene film βG2β can be reduced, and the edge state-induced characteristics can be made more detectable.
The protective film βT3β is provided on the third graphene film βG3β in such a manner that the edge of the third graphene film βG3β that is parallel with the second direction βBβ and the edge of the third graphene film βG3β that is opposed to the edge that is parallel with the second direction βBβ are exposed.
The protective film βT3β prevents the detection target substance or the liquid containing the detection target substance from coming into contact with the part of the surface of the third graphene film βG3β that is covered with the protective film βT3β.
As a result, the bulk conduction-induced characteristics of the third graphene film βG3β can be reduced, and the edge state-induced characteristics can be made more detectable.
No protective film is provided on the fourth graphene film βG4β.
Therefore, for the fourth graphene film βG4β, the bulk conduction-induced characteristics is detected along with the edge state-induced characteristics.
A method of manufacturing the biosensor according to this embodiment differs from the method of manufacturing the biosensor according to the first embodiment in that, following the step shown in FIG. 8 according to the first embodiment, the method further includes steps of forming the protective films βT1β to βT3β on the first to third graphene films βG1β to βG3β in such a manner that the edges of the first to third graphene films βG1β to βG3β that are parallel with the second direction βBβ and the edges of the first to third graphene films βG1β to βG3β that are opposed to the edges that are parallel with the second direction βBβ are exposed.
In other respects, the configuration of the biosensor shown in FIG. 15 and the method of manufacturing the biosensor are the same as those of the biosensor shown in FIG. 5.
The remainder of the characteristics of the operation of the biosensor is the same as that in the first embodiment.
That is, the biosensor according to this embodiment can detect a detection target substance with high sensitivity.
While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
1. A sensor that detects a detection target substance, comprising: an insulating layer; a first graphene film that is provided on the insulating layer so as to be located in a flow path of a liquid containing the detection target substance, the first graphene film having a first edge that is parallel with a first direction that is along the flow path and a second edge that is parallel with a second direction that is different from the first direction, and the first graphene film having the shape of a band that extends in the second direction; a first electrode that is electrically connected to the first edge of the first graphene film that is parallel with the first direction; and a second electrode that is electrically connected to a third edge of the first graphene film that is opposed to the first edge that is parallel with the first direction.
2. The sensor according to claim 1, wherein a width of the first graphene film in the first direction is equal to or smaller than a first prescribed value previously set, and the first prescribed value is 100 nm.
3. The sensor according to claim 1, wherein the second edge of the first graphene film that is parallel with the second direction and a fourth edge of the first graphene film that is opposed to the second edge that is parallel with the second direction are zigzag edges.
4. The sensor according to claim 1, wherein the second edge of the first graphene film that is parallel with the second direction and a fourth edge of the first graphene film that is opposed to the second edge that is parallel with the second direction are armchair edges.
5. The sensor according to claim 1,
wherein the insulating layer is provided on a substrate, and
wherein the first direction and the second direction are perpendicular to each other in a plane that is parallel with an upper surface of the substrate.
6. The sensor according to claim 1, further comprising:
a protective film that is provided on the first graphene film in such a manner that the second edge of the first graphene film that is parallel with the second direction and a fourth edge that is opposed to the second edge that is parallel with the second direction are exposed,
wherein the protective film prevents the liquid containing the detection target substance from coming into contact with a part of a surface of the first graphene film that is covered with the protective film.
7. The sensor according to claim 2, further comprising:
a second graphene film that is provided on the insulating layer so as to be located in the flow path and has the shape of a band that extends in the second direction; a third electrode that is electrically connected to a first edge of the second graphene film that is parallel with the first direction; and a fourth electrode that is electrically connected to a second edge of the second graphene film that is opposed to the first edge that is parallel with the first direction, wherein a width of the second graphene film in the first direction is equal to or smaller than the first prescribed value and is different from the width of the first graphene film in the first direction.
8. The sensor according to claim 7, further comprising:
a third graphene film that is provided on the insulating layer so as to be located in the flow path and has the shape of a band that extends in the second direction,
wherein: a width of the third graphene film in the first direction is equal to or smaller than the first prescribed value, the first electrode is electrically connected to a first edge of the third graphene film that is parallel with the first direction, and the second electrode is electrically connected to a second edge of the third graphene film that is opposed to the first edge that is parallel with the first direction.
9. The sensor according to claim 8, further comprising:
a fourth graphene film that is provided on the insulating layer so as to be located in the flow path and has the shape of a band that extends in the second direction;
a fifth electrode that is electrically connected to a first edge of the fourth graphene film that is parallel with the first direction; and a sixth electrode that is electrically connected to a second edge of the fourth graphene film that is opposed to the first edge that is parallel with the first direction, wherein a width of the fourth graphene film in the first direction is equal to or greater than a second prescribed value that is greater than the first prescribed value.
10. The sensor according to claim 9, wherein the second prescribed value is equal to or greater than 1 ΞΌm.
11. The sensor according to claim 1, wherein the first electrode and the second electrode contain any of Al, Cu, W and Ni.
12. The sensor according to claim 1, wherein the insulating layer is a silicon oxide film.
13. The sensor according to claim 1, wherein:
the first electrode is provided on the insulating layer and the first edge of the first graphene film that is parallel with the first direction, and the second electrode is provided on the insulating layer and the third edge of the first graphene film that is opposed to the first edge that is parallel with the first direction.
14. The sensor according to claim 1, further comprising:
a first side wall insulating layer that is provided on the insulating layer along the first direction on a right side of the flow path; a second side wall insulating layer that is provided on the insulating layer along the first direction on a left side of the flow path; and an upper insulating layer that is provided above the flow path along the first direction and is connected to upper parts of the first and second side wall insulating layers.
15. A method of manufacturing a sensor that detects a detection target substance, comprising: forming an insulating layer on a substrate; forming a first graphene film on the insulating layer so as to be located in a flow path of a liquid containing the detection target substance, the first graphene film having a first edge that is parallel with a first direction that is along the flow path and a second edge that is parallel with a second direction that is different from the first direction, and the first graphene film having the shape of a band that extends in the second direction; and forming a first electrode that is electrically connected to the first edge of the first graphene film that is parallel with the first direction and a second electrode that is electrically connected to a third edge of the first graphene film that is opposed to the first edge that is parallel with the first direction.
16. The method of manufacturing a sensor according to claim 15, wherein a width of the first graphene film in the first direction is equal to or smaller than a first prescribed value previously set, and the first prescribed value is 100 nm.
17. The method of manufacturing a sensor according to claim 15, further comprising:
forming a protective film on the first graphene film in such a manner that the second edge of the first graphene film that is parallel with the second direction and a fourth edge that is opposed to the second edge that is parallel with the second direction are exposed.
18. The method of manufacturing a sensor according to claim 16, further comprising:
forming a second graphene film on the insulating layer so as to be located in the flow path, the second graphene film having the shape of a band that extends in the second direction; forming a third electrode that is electrically connected to a first edge of the second graphene film that is parallel with the first direction and a fourth electrode that is electrically connected to a second edge of the second graphene film that is opposed to the first edge that is parallel with the first direction, wherein a width of the second graphene film in the first direction is equal to or smaller than the first prescribed value and is different from the width of the first graphene film in the first direction.
19. The method of manufacturing a sensor according to claim 15, further comprising:
forming a first side wall insulating layer on the insulating layer along the first direction on a right side of the flow path, a second side wall insulating layer on the insulating layer along the first direction on a left side of the flow path, and an upper insulating layer that is provided above the flow path along the first direction and is connected to upper parts of the first and second side wall insulating layers.
20. The method of manufacturing a sensor according to claim 15, wherein the first direction and the second direction are perpendicular to each other in a plane that is parallel with an upper surface of the substrate.