CN108303122A - The bionical optical detector of graphene and preparation method thereof based on thermoregulation energy - Google Patents

Abstract

The present invention provides a kind of bionical optical detector of graphene and preparation method thereof based on thermoregulation energy, and the preparation method includes：1) graphene and micro-heater platform are provided, and the graphene is transferred on the micro-heater platform；2) the obtained structure of step 1) is placed in chemical vapour deposition reactor furnace and is annealed；3) graphene surface after annealing is modified by reagent, forms the active film of active group；4) light receptor albumen is formed in the active film surface.The present invention connects graphene by using the heating structure of outstanding membrane type, and modifies light receptor albumen on the surface of graphene, on the one hand light receptor albumen is used to realize wavelength selectivity, improves absorptivity；On the other hand using membrane type heating structure is hanged, influence of the substrate to graphene performance is reduced, more operating temperature can be adjusted by heating voltage, to adjust photo-generated carrier mobility and concentration, to improve the performance of light-detecting device.

Description

Graphene bionic photodetector based on temperature regulation performance and its preparation method

technical field

The invention belongs to the technical field of photoelectric detection, and in particular relates to a graphene bionic photodetector based on temperature regulation performance and a manufacturing method thereof.

Background technique

Photodetectors are widely used in daily life and military fields, and photodetectors in different bands have different applications. The ultraviolet band is used to observe changes in the intensity of ultraviolet rays in the lower atmosphere on the ground, solar physics, and research on impending earthquake prediction; the visible or near-infrared band is used for ray measurement and detection, industrial automatic control, photometry, etc.; the infrared band is used for missile guidance, infrared thermal Imaging, infrared remote sensing, etc. Photodetectors in different wavelength bands are of great significance to different fields.

Photoreceptor proteins are light-sensitive biomolecules that cover wavelengths from the infrared region to the ultraviolet region. They have the characteristics of good wavelength selectivity, fast response to light, and high absorption rate. Photosensors prepared using photoreceptor proteins will have simpler structures, lower manufacturing costs and higher sensitivity than traditional photodetectors.

Although traditional photodetectors made of semiconductor materials have excellent performance, they are difficult to prepare materials, have high requirements on the working environment, and the cost of the detector is high. As a unique two-dimensional material, graphene has ultra-high carrier mobility and ultra-broad optical absorption spectrum (from ultraviolet to far-infrared) at room temperature, making it ideal for high-speed, wide-spectrum and low-cost photodetection. great potential. In addition, graphene's ultra-high specific surface area and excellent conductivity make it a good electron transport channel between the redox center of enzymes or proteins and the electrode surface. By modifying target molecules on graphene, electrons can be transferred quickly and selective detection of biomolecules can be realized, so graphene is also an ideal material for preparing biosensors.

However, graphene also has obvious disadvantages when used in light detection: intrinsic graphene has a low absorption rate of light and lacks an optical gain mechanism, resulting in a low photoresponsivity of the device; graphene itself has a short lifetime of photogenerated carriers. It is only about picoseconds, which makes it difficult to effectively collect photogenerated carriers, and also seriously affects the photoresponsivity of the detector. The low responsivity of graphene detectors cannot meet the needs of practical applications. In addition, the substrate material will significantly affect the properties of graphene. For example, the impurity and phonon vibration of the _SiO2 substrate will cause carrier scattering in graphene and seriously reduce the mobility of graphene carriers; graphene The interaction of phonons and substrate phonons reduces its thermal conductivity by a fifth of that of intrinsic graphene. Therefore, improving the mobility of carriers is of great significance for graphene photodetection.

Therefore, how to simply and efficiently increase the concentration and mobility of photogenerated carriers and improve the sensitivity of devices is a technical problem that those skilled in the art are eager to solve.

Contents of the invention

In view of the shortcomings of the prior art described above, the object of the present invention is to provide a method for regulating the performance of graphene bionic photodetectors by temperature, in order to solve the problems of low absorption rate and low sensitivity of graphene photodetectors at the present stage. question.

In order to achieve the above object and other related objects, the invention provides a method for preparing a graphene bionic photodetector based on temperature regulation performance, which is characterized in that, comprising the steps of:

1) Graphene and a micro heater platform are provided, and the graphene is transferred to the micro heater platform;

2) placing the structure obtained in step 1) in a chemical vapor deposition reaction furnace for annealing;

3) using reagents to modify the annealed graphene surface to form an active film with active groups on the graphene surface;

4) forming a photoreceptor protein on the surface of the active film, and combining the photoreceptor protein with the active group of the active film to form a covalent bond to connect the photoreceptor protein and the active film.

As a preferred solution of the present invention, in step 1), the micro-heater platform is made in the following steps:

1-1) A substrate is provided, and a composite film is formed on the substrate, and the composite film is used to define a heating film area and a support beam area;

1-2) forming a heating metal layer on the composite film, and patterning the heating metal layer to obtain a resistance device, the resistance device comprising a heating resistance wire, a first power supply lead, a first power supply electrode, at least the The heating resistance wire is located in the heating film area;

1-3) forming an insulating layer on the heating metal layer;

1-4) forming a test metal layer on the insulating layer, and patterning the test metal layer to obtain an electrode device, the electrode device includes a test electrode, a second power supply lead, a second power supply electrode, at least the The test electrode is set up and down corresponding to the heating resistance wire, and in addition, the graphene at least covers the test electrode;

1-5) forming a film release window in the structure formed in step 1-4), and exposing the substrate;

1-6) Etching part of the substrate through the thin film release window to form a heat-insulating cavity, so as to release the heating film region and the supporting beam region.

As a preferred solution of the present invention, in step 1-1), the substrate is a silicon substrate on the (100) plane, and the composite film is formed of at least one silicon oxide film and at least one silicon nitride film composite film.

As a preferred solution of the present invention, in step 1-4), the test electrodes are interdigital electrodes.

As a preferred solution of the present invention, in step 1-6), the shape of the support beam area is straight or serpentine.

As a preferred solution of the present invention, in step 1), the graphene is transferred to the micro heater platform by direct transfer method or PMMA method.

As a preferred version of the present invention, step 2) specifically includes:

2-1) using an inert gas to ventilate and exhaust the reaction furnace;

2-2) Passing an inert gas into the reaction furnace at a first temperature;

2-3) Passing inert gas and hydrogen into the reaction furnace at the second temperature at the same time;

2-4) Reduce the flow rate of the inert gas and the hydrogen, and lower the temperature of the reaction furnace.

As a preferred solution of the present invention, in step 2-1), the flow rate of the inert gas is 500sccm-2000sccm, and the aeration and exhaust treatment time is 2min-3min;

As a preferred solution of the present invention, in step 2-2), the first temperature is 200°C-300°C, and the flow rate of the inert gas is 500sccm-2000sccm.

As a preferred solution of the present invention, in step 2-3), the second temperature is 300°C to 400°C, and is kept at the second temperature for 5min to 10min, and the hydrogen gas and the The total flow rate of the mixed gas of the inert gas is 500sccm-2000sccm, the volume fraction of the hydrogen in the mixed gas is 30%-50%, and the time for feeding the inert gas and the hydrogen is 40min-120min.

As a preferred solution of the present invention, in step 2-4), the flow rate of the inert gas is 50 sccm-200 sccm, the flow rate of the hydrogen gas is 10 sccm-40 sccm, and the cooling method is natural cooling of the reaction furnace.

As a preferred version of the present invention, in step 3), the reagents include 1,5-diaminonaphthalene, 1-pyrenebutyric acid, glutaraldehyde, 1-(3-dimethylaminopropyl)-3- One or more combinations of ethyl carbodiimide hydrochloride and N-hydroxysuccinimide; the active groups are amino active groups, carboxyl active groups, and aldehyde active groups one or a combination of two or more.

As a preferred solution of the present invention, in step 4), the photoreceptor proteins include opsins, photochromes, cryptochromes, phototropes, BLUF domains, and ultraviolet light receptors. one or a combination of two or more.

As a preferred solution of the present invention, it includes: micro-heater platform; graphene, located on the micro-heater platform; active film, formed on the surface of the graphene; photoreceptor protein, formed on the active on the film.

As a preferred solution of the present invention, the micro heater platform includes sequentially from bottom to top:

a substrate comprising a thermally isolated cavity;

a composite film, located above the heat insulation cavity, including a heating film area and a support beam area, the support beam area connecting the heating film area and the substrate;

A resistance device, including a heating resistance wire, a first power supply lead, and a first power supply electrode, wherein at least the heating resistance wire is formed on the heating film region;

an insulating layer, formed on the resistance device, covering at least the heating resistance wire;

The electrode device is formed on the insulating layer, and includes a test electrode, a second power supply lead, and a second power supply electrode, wherein at least the test electrode is arranged correspondingly up and down with the heating resistance wire, and the graphene covers at least the the test electrodes.

As a preferred solution of the present invention, the test electrodes are interdigital electrodes.

As a preferred solution of the present invention, the active film is an active film with active groups, and the photoreceptor protein combines with the active groups of the active film to form a covalent bond to connect the photoreceptor protein and the active film.

As mentioned above, the graphene biomimetic photodetector based on the temperature adjustment performance of the present invention and its preparation method have the following beneficial effects:

1) The test electrode of the present invention is located at the corresponding place of the heating film area, and is used to connect the graphene, build a built-in electric field, and drive the flow of photogenerated carriers, thereby enhancing the response signal;

2) The suspended film heating structure is used to provide the temperature required for the sensor to work, reducing the influence of the substrate on the performance of graphene, and enriching the heat through the suspended film structure, which is beneficial to improve the uniformity of the temperature, and is easy to adjust and control the work Temperature to improve sensor performance;

3) The photoreceptor protein is used to achieve wavelength selectivity, improve the light absorption rate, solve the problem that the wavelength bands of intrinsic graphene photodetectors are difficult to distinguish, and the preparation is simple, the cost is low, and it is suitable for mass production;

Description of drawings

FIG. 1 shows a flow chart of a method for preparing a graphene bionic photodetector based on temperature regulation performance provided by Embodiment 1 of the present invention.

Fig. 2a-2l shows the structure schematic diagram in each step of the preparation method of the graphene biomimetic photodetector based on the temperature adjustment performance provided in the embodiment of the present invention, wherein, Fig. 2h is the sectional view of Fig. 2i, and Fig. 2j is a diagram An exploded view of the 2i structure.

Component designation description

1 Micro heater platform

11 Substrate

12 Composite film

13 Heating the metal layer

130 Resistive Devices

131 heating resistance wire

132 First supply lead

133 first power supply electrode

14 insulation layer

15 Test metal layer

150 electrode device

151 Test electrode

152 Second supply lead

153 Second supply electrode

16 Film release window

17 Insulation cavity

2 Graphene

3 active groups

4 photoreceptor proteins

S11～S14 steps

Detailed ways

Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation modes, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.

See Figures 1 to 2l. It should be noted that the diagrams provided in this embodiment are only schematically illustrating the basic concept of the present invention, although only the components related to the present invention are shown in the diagrams rather than the number, shape and Dimensional drawing, the type, quantity and proportion of each component can be changed arbitrarily during actual implementation, and the layout of the components may also be more complicated.

Embodiment one

Please refer to Fig. 1, the present invention provides a kind of preparation method based on the graphene biomimetic photodetector of temperature regulating performance, it is characterized in that, comprises the steps:

1) Graphene and a micro heater platform are provided, and the graphene is transferred to the micro heater platform;

2) placing the structure obtained in step 1) in a chemical vapor deposition reaction furnace for annealing;

3) using reagents to modify the annealed graphene surface to form an active film with active groups on the graphene surface;

4) forming a photoreceptor protein on the surface of the active film, and combining the photoreceptor protein with the active group of the active film to form a covalent bond to connect the photoreceptor protein and the active film.

In step 1), please refer to S1 step among Fig. 1 and Fig. 2a, provide graphene 2 and micro heater platform 1, and described graphene 2 is transferred on the described micro heater platform 1;

Specifically, in this embodiment, the graphene 2 is single-layer graphene, and in other embodiments, it may also be double-layer or multi-layer graphene. In addition, preferably, the graphene 2 may be, but not limited to, graphene grown on a copper substrate. Further, the graphene 2 described in this embodiment is intrinsic graphene, but it is not limited thereto.

As an example, the graphene is transferred onto the electrode device using a direct transfer method or a PMMA (polymethyl methacrylate) method.

Specifically, taking the direct transfer method as an example, the transfer of the graphene to the electrode device includes the following steps: first, the copper substrate with the graphene 2 grown on the surface is placed in an etching solution for 2 h, The corrosion solution is Fe(NO ₃ ) ₃ solution or FeCl ₃ solution with a certain concentration (for example, the concentration is 0.1g/ml), so that the graphene 2 is separated from the copper substrate; The graphene 2 is scooped up.

Specifically, after using Fe(NO ₃ ) ₃ solution or FeCl ₃ solution to separate the graphene 2 from the copper substrate, before using the micro heater platform to pick up the graphene 2, it may also include The step of corroding the graphene 2 in an HCl solution with a certain molar concentration (eg, 10% molar concentration) for 1 hour to remove copper remaining on the surface of the graphene 2 .

Meanwhile, the preparation method of the micro heater platform described in step 1) is specifically:

Referring to Fig. 2b-2c, at first carry out step 1-1), provide a substrate 11, and form composite film 12 on described substrate 11, described composite film is used for defining heating film region (not shown in the figure Out) and supporting beam area (not shown in the figure);

As an example, in step 1-1), the substrate 11 is a silicon substrate with a (100) plane, or may be an SOI substrate, so as to increase the operating speed of the internal circuits of the device. The composite film 12 is a composite film formed of at least one silicon oxide film and at least one silicon nitride film.

Specifically, after the composite film 12 is patterned in a subsequent process, the heating film region and the support beam region are defined. The composite film 12 is formed on the substrate 11 by methods such as oxidation, plasma enhanced chemical vapor deposition (PECVD), or low pressure chemical vapor deposition (LPCVD). In other embodiments, the composite film 12 can also be nitrogen-doped porous, silicon carbide, etc., these materials have a good self-stopping effect on the anisotropic wet etching of silicon, in addition, their thermal conductivity is very small, and the fabricated The heat insulation performance of the support beam area is good, and the heat loss generated is low.

Preferably, the preparation process of the composite film 12 is as follows: First, a layer of silicon oxide with a thickness of 0.1 μm to 0.5 μm (0.2 μm in this embodiment) and a layer of silicon oxide with a thickness of 0.1 μm are sequentially deposited by low-pressure chemical vapor deposition (LPCVD). μm to 0.5 μm (0.2 μm in this embodiment); secondly, a layer of silicon nitride with a thickness of 0.1 μm to 0.5 μm (0.2 μm in this embodiment) is sequentially deposited by plasma enhanced chemical vapor deposition (PECVD). Silicon oxide and a layer of silicon nitride with a thickness of 0.1 μm to 0.5 μm (0.2 μm in this embodiment). Furthermore, if the composite film is formed of two or more layers of silicon oxide films and two or more layers of silicon nitride films, it is preferable that the silicon oxide films and the silicon nitride films are alternately stacked.

As an example, the shape of the support beam area is straight or serpentine.

Specifically, the length of the support beam region can be increased by bending the structure, such as adopting a serpentine design, which helps to reduce the heat conduction of the support beam region.

Please refer to Fig. 2d, carry out step 1-2), make heating metal layer 13 on described composite film 12, and pattern out resistance device 130 on described heating metal layer 13, described resistance device comprises heating resistance wire 131 , the first power supply lead 132, the first power supply electrode 133;

Specifically, the material of the heating metal layer 13 is Ti/Au or Ti/Pt, and the thickness of the heating metal layer 13 is 30 nm to 300 nm. In this embodiment, the thickness of the heating metal layer 13 is 100 nm. In addition, the patterning method is to use lift-off or wet etching process, wherein, the heating resistance wire 131 is preferably a serpentine heating resistance wire, so that its size can be reasonably arranged, and the uniformity of temperature distribution can be increased. Heating resistance wires of other shapes can be used, and there is no limitation here. In addition, the first electrode lead 132 is connected to the heating resistance wire 131 and the first power supply electrode 133 , and the first power supply lead 132 is preferably located on the surface of the support beam area.

Please refer to FIG. 2e, perform steps 1-3), and form an insulating layer 14 on the heating metal layer 13;

Specifically, the insulating layer 14 is a silicon nitride insulating layer formed on the heating metal layer 13 by plasma enhanced chemical vapor deposition (PECVD). Wherein, the thickness of the silicon nitride insulating layer is 400nm-600nm, and in this embodiment, preferably 500nm.

Referring to FIG. 2f, perform steps 1-4), form a test metal layer 15 on the insulating layer 14, and pattern an electrode device 150 on the test metal layer 15, and the electrode device 150 includes a test electrode 151 , the second power supply lead 152, the second power supply electrode 153, at least the test electrode 151 and the heating resistance wire 131 are set up and down correspondingly, in addition, the graphene 2 at least covers the test electrode 151;

As an example, the test electrodes 151 are interdigital electrodes.

Specifically, the material of the test metal layer 15 is Ti/Au or Ti/Pt, and the thickness of the test metal layer 15 is 30 nm to 300 nm. In this embodiment, the thickness of the test metal layer 15 is 100 nm. In addition, the forming method of the electrode device 150 is a lift-off or wet etching process. In addition, the second electrode lead 152 is connected to the test electrode 151 and the second power supply electrode 153 , and the second power supply lead 152 is preferably located at a position corresponding to the support beam area.

Preferably, in this embodiment, the test electrode 151 is an interdigital electrode, wherein the interdigital electrode is located at a position corresponding to the heating film region, and is used to connect graphene, and the interdigital electrode is used to construct a built-in electric field, The flow of photo-generated carriers is more effectively driven, so that the response signal is enhanced. Of course, electrodes of other shapes, such as serpentine electrodes, etc., are also possible, which are not limited here.

Referring to FIG. 2g, perform steps 1-5), form a film release window 16 in the structure formed in steps 1-4), and expose the substrate 11;

Specifically, in the process of forming the film release window 16, the electrode devices (including the test electrode 151, the second power supply lead 152, the second power supply electrode 153) and the resistance device (including the heating resistance wire 131, first power supply lead 132 , first power supply electrode 133 ), and remove the exposed insulating layer 14 and the composite film 12 . Preferably, a heating film area and a support beam area are patterned in the composite film 12, and the support beam area at least supports the heating resistance wire 131 and the test electrode 151, and connects the heating film area and the The substrate 11;

Please refer to Fig. 2h-2j, perform step 1-6), corrode part of the substrate 11 through the thin film release window 16 to form a thermal insulation cavity 17, so as to release the heating film area and the support beam area;

Specifically, in step 1-6), the substrate 11 is etched with an anisotropic etching solution, such as tetramethylammonium hydroxide (TMAH) or potassium hydroxide (KOH), etc. , so as to hollow out the substrate under the composite membrane 12, release the thin film structure, and obtain a device with a suspended membrane structure. Preferably, the heat insulation cavity 17 is a heat insulation cavity such as an inverted trapezoid. The micro-heater platform with a suspended film heating structure formed through the above steps can reduce the influence of the substrate on the performance of graphene, and can also control the working temperature by adjusting the heating voltage, thereby adjusting the mobility and concentration of photogenerated carriers. To improve the performance of photodetection devices.

It should be noted that the heating structure (micro-heater platform) of the suspension film type provided in the second embodiment is used to provide the temperature required for the sensor to work, and the temperature is adjusted by changing the voltage at both ends of the heating resistance wire 131. The structure is rich in heat, which is conducive to improving the uniformity of temperature, and it is easy to improve the performance of the sensor by adjusting and controlling the working temperature. And when light is irradiated on the graphene 2 of the cured photoreceptor protein 4, the generation of photogenerated carriers causes the resistance of the device to change, and light detection can be realized by measuring the resistance change between the detection electrodes.

In step 2), please refer to S12 shown in Figure 1, place the structure obtained in step 1) in a chemical vapor deposition reaction furnace for annealing;

As an example, step 2) specifically includes:

2-1) using an inert gas to ventilate and exhaust the reaction furnace;

2-2) Passing an inert gas into the reaction furnace at a first temperature;

2-3) Passing inert gas and hydrogen into the reaction furnace at the second temperature at the same time;

2-4) Reduce the flow rate of the inert gas and the hydrogen, and lower the temperature of the reaction furnace.

Specifically, after the above annealing process, the surface of the graphene 2 has no oxygen-containing functional groups, and the graphene 2 with a clean surface can be obtained.

As an example, in step 2-1), the flow rate of the inert gas is 500 sccm-2000 sccm, and the ventilation and exhaust treatment time is 2 min-3 min.

Specifically, in this embodiment, the flow rate of the inert gas is 1000 sccm, and the ventilation and exhaust treatment time is 2.5 minutes.

As an example, in step 2-2), the first temperature is 200° C. to 300° C., and the flow rate of the inert gas is 500 sccm to 2000 sccm.

Specifically, in this embodiment, the first temperature is 250° C., and the flow rate of the inert gas is 1000 sccm.

As an example, in step 2-3), the second temperature is 300°C to 400°C. Preferably, the second temperature is kept at the second temperature for 5min to 10min, and the hydrogen and the inert The total flow rate of the mixed gas is 500sccm-2000sccm, the volume fraction of the hydrogen in the mixed gas is 30%-50%, and the time for feeding the inert gas and the hydrogen is 40min-120min.

Specifically, in this embodiment, the second temperature is 350° C., and is maintained at the second temperature for 8 minutes. After the heat preservation, the total flow rate of the mixed gas of the hydrogen gas and the inert gas is 1000 sccm, The volume fraction of the hydrogen in the mixed gas is 40%, and the time for feeding the inert gas and the hydrogen is 80 minutes.

As an example, in step 2-4), the flow rate of the inert gas is 50 sccm-200 sccm, the flow rate of the hydrogen gas is 10 sccm-40 sccm, and the cooling method is preferably the natural cooling of the reaction furnace.

Specifically, in this embodiment, the flow rate of the inert gas is 100 sccm, and the flow rate of the hydrogen gas is 30 sccm.

In step 3), please refer to S13 and FIG. 2k in FIG. 1, use reagents to modify the surface of the annealed graphene 2 to form an active film with active groups 3 on the surface of the graphene 2 ( not shown in the figure);

As an example, in step 3), the reagents include 1,5-diaminonaphthalene, 1-pyrenebutyric acid, glutaraldehyde, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide One or more combinations of hydrochloride and N-hydroxysuccinimide; the active group is one or two of amino active groups, carboxyl active groups, and aldehyde active groups combination of the above.

Specifically, after treatment with the above reagents, preferably, an active film terminated with a group corresponding to the corresponding reagent can be obtained, so as to facilitate the connection of the photoreceptor protein 4.

Specifically, the active group is one or a combination of two or more of amino active groups, carboxyl active groups, and aldehyde active groups. In other embodiments, it can also be a The same or similar reactive film with other reactive groups.

In step 4), please refer to S14 in Fig. 1 and shown in Fig. 21, photoreceptor protein 4 is formed on the surface of the active film (not shown in the figure), and the photoreceptor protein 4 and the active The active group 3 of the film combines to form a covalent bond to connect the photoreceptor protein 4 with the active film.

As an example, the photoreceptor protein 4 includes opsin-like photoreceptor proteins, phytochrome-like photoreceptor proteins, cryptochrome-like photoreceptor proteins, phototropic pigment-like photoreceptor proteins, and BLUF domain-like photoreceptor proteins. One or a combination of two or more of receptor proteins and ultraviolet light receptor-like photoreceptor proteins.

Specifically, through the above step 6), the photoreceptor protein 4 is modified on the surface of the graphene 2 to obtain a graphene bionic photodetector based on temperature regulation performance. The photoreceptor protein is used to achieve wavelength selectivity and increase the light absorption rate, and the photosensor prepared by using the photoreceptor protein will have a simpler structure, lower manufacturing cost and higher sensitivity than traditional photodetectors.

Embodiment two

Please refer to Fig. 2l, the present invention also provides a graphene bionic photodetector based on temperature regulation performance, which is prepared by the preparation method in the scheme of embodiment 1. The graphene bionic photodetector based on the temperature regulation performance includes: a micro heater platform 1; Graphene 2, located on the micro heater platform 1; active film (not shown in the figure), formed on the graphene 2; photoreceptor protein 4, formed on the active film.

As an example, the micro heater platform 1 includes sequentially from bottom to top:

a substrate 11, which includes a thermally-insulated cavity 17;

Composite film 12, located above the heat insulation cavity 17, includes a heating film area and a supporting beam area, and the supporting beam area connects the heating film area and the substrate 11;

The resistance device 130 includes a heating resistance wire 131, a first power supply lead 132, and a first power supply electrode 133, wherein at least the heating resistance wire 131 is formed on the heating film area;

an insulating layer 14, formed on the resistance device 130, covering at least the heating resistance wire 131;

The electrode device 150 is formed on the insulating layer 14, and includes a test electrode 151, a second power supply lead 152, and a second power supply electrode 153, wherein at least the test electrode 151 is set corresponding to the heating resistance wire 131, so The graphene 2 at least covers the test electrode 151 .

Preferably, the composite film 12 is a composite film formed of at least one silicon oxide film and at least one silicon nitride film. Further preferably, the composite film 12 is as follows: first, a layer of silicon oxide with a thickness of 0.1 μm to 0.5 μm (0.2 μm in this embodiment) and a layer of silicon oxide with a thickness of 0.1 μm to 0.5 μm (0.2 μm in this embodiment) of silicon nitride; followed by plasma-enhanced chemical vapor deposition (PECVD) to deposit a layer of silicon oxide and A layer of silicon nitride with a thickness of 0.1 μm to 0.5 μm (0.2 μm in this embodiment). Furthermore, if the composite film is formed of two or more layers of silicon oxide films and two or more layers of silicon nitride films, it is preferable that the silicon oxide films and the silicon nitride films are alternately stacked.

Specifically, the thickness of the electrode device 150 is 30 nm to 300 nm. In this embodiment, the thickness of the electrode device 150 is preferably 100 nm. The silicon nitride insulating layer has a thickness of 400 nm to 600 nm, preferably 500 nm in this embodiment.

As an example, the test electrodes 151 are interdigital electrodes.

Specifically, the test electrode 151 is an interdigital electrode, wherein the interdigital electrode is used to construct a built-in electric field to drive the flow of photo-generated carriers more effectively, so that the response signal is enhanced. Of course, it can also be an electrode of other shapes, Such as serpentine electrodes, etc., are not limited here.

As an example, the active film is an active film with an active group 3, and the photoreceptor protein 4 combines with the active group 3 of the active film to form a covalent bond to connect the photoreceptor protein 4 and the active film.

Specifically, the active film ends with the active group, so as to connect the photoreceptor protein 4, and the active group is an amino active group, a carboxyl active group, and an aldehyde active group. A combination of one or more than two, in other embodiments, can also be an active film with other active groups that can achieve the same or similar function as this step.

Specifically, the photoreceptor protein 4 is modified on the surface of the graphene 2 to obtain a graphene bionic photodetector based on temperature regulation performance. The photoreceptor protein is used to achieve wavelength selectivity and increase the light absorption rate, and the photosensor prepared by using the photoreceptor protein will have a simpler structure, lower manufacturing cost and higher sensitivity than traditional photodetectors.

In summary, the present invention provides a graphene bionic photodetector based on temperature regulation performance and a preparation method thereof, the preparation method comprising the following steps: 1) providing a graphene and a micro-heater platform, and the graphite 2) place the structure obtained in step 1) in a chemical vapor deposition reactor for annealing; 3) use reagents to modify the surface of the annealed graphene, so that Form an active film with an active group on the surface of the graphene; 4) form a photoreceptor protein on the surface of the active film, and the photoreceptor protein combines with the active group of the active film to form a covalent bond to connect The photoreceptor protein and the active film. Based on the above scheme, the present invention connects graphene by adopting a suspended film heating structure, and modifies photoreceptor protein on the surface of graphene. On the one hand, photoreceptor protein is used to realize wavelength selectivity and improve light absorption rate; The suspended film heating structure reduces the influence of the substrate on the performance of graphene, and the working temperature can be adjusted by heating voltage, thereby adjusting the mobility and concentration of photogenerated carriers to improve the performance of photodetection devices.

The above-mentioned embodiments only illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed in the present invention should still be covered by the claims of the present invention.

Claims (17)

1. a kind of preparation method of the bionical optical detector of graphene based on thermoregulation energy, which is characterized in that including as follows Step：

1) graphene and micro-heater platform are provided, and the graphene is transferred on the micro-heater platform；

2) structure that step 1) obtains is placed in chemical vapour deposition reactor furnace and is annealed；

3) graphene surface after annealing is modified using reagent, it is active to be formed in the graphene surface The active film of group；

4) light receptor albumen, the active group of the light receptor albumen and the active film are formed in the active film surface In conjunction with covalent bond is formed, to connect the light receptor albumen and the active film.

2. the preparation method of the graphene bionical optical detector according to claim 1 based on thermoregulation energy, special Sign is, in step 1), the micro-heater platform is made of following steps：

A substrate 1-1) is provided, and in forming composite membrane on the substrate, the composite membrane is for defining heating film region and branch The areas Cheng Liang；

1-2) in formation heating metal layer on the composite membrane, and by the heating metallic layer graphic to obtain resistance device, The resistance device includes resistive heater, first for electrical lead, the first current electrode, and at least described resistive heater is located at institute State heating film region；

1-3) in forming insulating layer on the heating metal layer；

1-4) in formation test metal layer on the insulating layer, and by the test metallic layer graphic to obtain electrode device, The electrode device includes test electrode, second for electrical lead, the second current electrode, at least described test electrode and the heating Resistance wire is correspondingly arranged up and down, in addition, the graphene at least covers the test electrode；

1-5) in step 1-4) film release window is formed in the structure that is formed, and expose the substrate；

1-6) by described in the film release window erodable section substrate formed heat-insulation chamber, with release the heating film region and Supporting beam area.

3. the preparation method of the graphene bionical optical detector according to claim 2 based on thermoregulation energy, special Sign is, step 1-1) in, the substrate is the silicon substrate in (100) face, and the composite membrane is at least one layer of silicon oxide film and extremely The composite membrane that few one layer of silicon nitride film is formed.

4. the preparation method of the graphene bionical optical detector according to claim 2 based on thermoregulation energy, special Sign is, step 1-4) in, the test electrode is interdigital electrode.

5. the preparation method of the graphene bionical optical detector according to claim 2 based on thermoregulation energy, special Sign is, step 1-6) in, the shape in the supporting beam area is linear or snakelike.

6. the preparation method of the graphene bionical optical detector according to claim 1 based on thermoregulation energy, special Sign is, in step 1), the graphene is transferred on the micro-heater platform using direct transfer process or PMMA methods.

7. the preparation method of the graphene bionical optical detector according to claim 1 based on thermoregulation energy, special Sign is that step 2) specifically includes：

2-1) inert gas is used to carry out ventilation and gas exhaust treatment to the reacting furnace；

2-2) inert gas is passed through into the reacting furnace at a temperature of first；

2-3) inert gas and hydrogen are passed through into the reacting furnace simultaneously under second temperature；

The flow of the inert gas and the hydrogen 2-4) is reduced, and is cooled down to the reacting furnace.

8. the preparation method of the graphene bionical optical detector according to claim 7 based on thermoregulation energy, special Sign is, step 2-1) in, the flow of the inert gas is 500sccm~2000sccm, when the ventilation and gas exhaust treatment Between be 2min~3min.

9. the preparation method of the graphene bionical optical detector according to claim 7 based on thermoregulation energy, special Sign is, step 2-2) in, first temperature is 200 DEG C~300 DEG C, the flow of the inert gas be 500sccm~ 2000sccm。

10. the preparation method of the graphene bionical optical detector according to claim 7 based on thermoregulation energy, special Sign is, step 2-3) in, the second temperature is 300 DEG C~400 DEG C, and keep under the second temperature 5min~ 10min, total flow 500sccm~2000sccm of the hydrogen being passed through after heat preservation and the mixed gas of the inert gas, The volume fraction of hydrogen described in the mixed gas is 30%~50%, is passed through the time of the inert gas and the hydrogen For 40min~120min.

11. the preparation method of the graphene bionical optical detector according to claim 7 based on thermoregulation energy, special Sign is, step 2-4) in, flow 50sccm~200sccm of the inert gas, the flow 10sccm of the hydrogen~ The mode of 40sccm, the cooling are reacting furnace Temperature fall.

12. the preparation method of the graphene bionical optical detector according to claim 1 based on thermoregulation energy, special Sign is, in step 3), the reagent includes 1,5-diaminonaphthalene, 1- pyrenes butyric acid, glutaraldehyde, 1- (3- dimethylamino-propyls)- The combination of one or more of 3- ethyl-carbodiimide hydrochlorides and n-hydroxysuccinimide；The active group is The combination of one or more of amino active group, carboxyl-reactive group, aldehyde radical active group.

13. the preparation method of the graphene bionical optical detector according to claim 1 based on thermoregulation energy, special Sign is, in step 4), the light receptor albumen include opsin class, phytochrome class, cryptochrome class, to photopigment class, The combination of one or more of BLUF structural domains class, ultraviolet light receptor class.

14. a kind of bionical optical detector of graphene based on thermoregulation energy, which is characterized in that including：

Micro-heater platform；

Graphene is located on the micro-heater platform；

Active film is formed in the surface of the graphene；

Light receptor albumen is formed on the active film.

15. the graphene bionical optical detector according to claim 14 based on thermoregulation energy, which is characterized in that institute Stating micro-heater platform includes successively from bottom to top：

Substrate, including a heat-insulation chamber；

Composite membrane is located above the heat-insulation chamber, including heating film region and supporting beam area, and the supporting beam area connection is described to be added Hotting mask area and the substrate；

Resistance device, including resistive heater, first are for electrical lead, the first current electrode, wherein at least described resistive heater It is formed on the heating film region；

Insulating layer, is formed on the resistance device, at least covers the resistive heater；

Electrode device is formed on the insulating layer, and includes test electrode, second for electrical lead, the second current electrode, In, at least described test electrode is correspondingly arranged up and down with the resistive heater, and the graphene at least covers the test electricity Pole.

16. the graphene bionical optical detector according to claim 15 based on thermoregulation energy, which is characterized in that institute It is interdigital electrode to state test electrode.

17. the graphene bionical optical detector according to claim 14 based on thermoregulation energy, which is characterized in that institute The active film that active film is active group is stated, the light receptor albumen is combined with the active group of the active film Covalent bond is formed, to connect the light receptor albumen and the active film.