CN108767068B - Two-dimensional material photodetector and manufacturing method thereof - Google Patents

Two-dimensional material photodetector and manufacturing method thereof Download PDF

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CN108767068B
CN108767068B CN201810587639.2A CN201810587639A CN108767068B CN 108767068 B CN108767068 B CN 108767068B CN 201810587639 A CN201810587639 A CN 201810587639A CN 108767068 B CN108767068 B CN 108767068B
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dimensional material
photosensitive
semiconductor substrate
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windows
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CN108767068A (en
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李绍娟
孙甜
马玮良
拓明芬
袁建
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Suzhou University
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    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract

The invention discloses a manufacturing method of a two-dimensional material photodetector, which is characterized by comprising the following steps of preparing a base, wherein the base comprises a semiconductor substrate and an insulating layer arranged on one surface of the semiconductor substrate, two symmetrical windows are formed in the insulating layer to expose the semiconductor substrate, a layer of photosensitive two-dimensional material is arranged on one surface, provided with the windows, of the base, so that the photosensitive two-dimensional material layer and the semiconductor substrate form a back-to-back double Schottky barrier, and two electrodes are manufactured on one surface, far away from the semiconductor substrate, of the photosensitive two-dimensional material layer. The back-to-back double Schottky barriers are formed by the semiconductor two-dimensional material and the semiconductor, when direct current bias voltage is applied, one barrier is forward biased, and the other barrier is reverse biased, so that the low dark current is achieved.

Description

Two-dimensional material photodetector and manufacturing method thereof
Technical Field
The invention relates to the field of two-dimensional material photodetectors, in particular to a two-dimensional material photodetector and a manufacturing method thereof.
Background
Two-dimensional materials refer to materials in which electrons can move freely only in two dimensions on a non-nanoscale, such as nano-films, superlattices, and quantum wells.
Graphene has significant advantages over traditional semiconductor materials in the aspect of optical detection as a novel photosensitive material, and has an extremely wide absorption spectrum due to a unique zero band gap energy band structure, and the optical detector based on graphene not only has an ultra-fast response speed, but also can realize ultra-wide band detection from ultraviolet, visible near infrared and even middle and far infrared. However, the graphene photodetector has a fatal weakness: the zero band gap structure of the graphene enables the recombination probability of photon-generated carriers to be very large, the dark current is also very large, the graphene light absorption rate of one atomic layer is low and is about 2.3%, the light responsivity of a corresponding device is very low, and high-sensitivity detection is not facilitated. Therefore, how to reduce the dark current of the device is a problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a manufacturing method for manufacturing a two-dimensional material photodetector with low dark current.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for manufacturing a two-dimensional material photodetector comprises the following steps,
a method for manufacturing a two-dimensional material photodetector is characterized by comprising the following steps,
s1, forming back-to-back double schottky barriers between the photosensitive two-dimensional material and the semiconductor, specifically including,
a. preparing a base including a semiconductor substrate and an insulating layer disposed on one side of the semiconductor substrate,
b. two symmetrical windows are opened on the insulating layer to expose the semiconductor substrate,
c. arranging a layer of photosensitive two-dimensional material on one surface of the substrate, which is provided with the window, to form a photosensitive two-dimensional material layer, wherein the photosensitive two-dimensional material layer covers the surface of the insulating layer and covers the whole exposed surface of the semiconductor substrate, so that the back-to-back double Schottky barrier formed by the photosensitive two-dimensional material layer and the semiconductor substrate,
and S2, manufacturing two electrodes on one surface of the photosensitive two-dimensional material layer far away from the semiconductor substrate, so that the two electrodes are respectively positioned on two sides of the symmetry axes of the two windows and the two windows are positioned between the two electrodes.
This application adopts semiconductor two-dimensional material and semiconductor to constitute two schottky barrier back to make this application have lower dark current.
Further, the method comprises the following steps: the method also comprises the step of carrying out the following steps,
and modifying the surface of the photosensitive two-dimensional material layer in one window forming the double Schottky barrier with a semiconductor two-dimensional material.
Further, the method comprises the following steps: the photosensitive two-dimensional material layer is graphene, MoS2, MoTe2, PtSe2, black phosphorus or Mo2C, and preferably, the photosensitive two-dimensional material layer is graphene.
Further, the method comprises the following steps: the semiconductor two-dimensional material is quantum dots, zinc oxide, titanium oxide nanosheets or titanium oxide nanowires.
Further, the method comprises the following steps: the semiconductor substrate is Si, Ge or GaN, the insulating layer is silicon dioxide, aluminum oxide, hafnium oxide or zirconium oxide, preferably, the semiconductor substrate is highly doped Si, and the insulating layer is silicon dioxide.
Further, the method comprises the following steps: the electrodes are symmetrical electrodes.
The application further provides a two-dimensional material optical detector, and the adopted technical scheme is as follows: the semiconductor substrate comprises a base, wherein the base comprises a semiconductor substrate and an insulating layer arranged on one surface of the semiconductor substrate, two symmetrical windows are formed in the insulating layer, the semiconductor substrate in each window is exposed, a photosensitive two-dimensional material layer is arranged on the surface, provided with the window, of the base, the photosensitive two-dimensional material layer covers the surface of the insulating layer and covers the whole surface of the exposed semiconductor substrate in each window, two electrodes are arranged on one surface, far away from the semiconductor substrate, of the photosensitive two-dimensional material layer, the two electrodes are located on two sides of the symmetrical axis of the two windows, and the two windows are located between the two electrodes.
Further, the method comprises the following steps: the surface of the photosensitive two-dimensional material layer in one of the windows is modified with a semiconductor two-dimensional material.
Further, the method comprises the following steps: the semiconductor two-dimensional material is quantum dots, zinc oxide, titanium oxide nanosheets or titanium oxide nanowires.
Further, the method comprises the following steps: the photosensitive two-dimensional material layer is graphene, MoS2, MoTe2, PtSe2, black phosphorus or Mo2C, the semiconductor substrate is Si, Ge or GaN, and the insulating layer is silicon dioxide, aluminum oxide, hafnium oxide or zirconium oxide.
The invention has the beneficial effects that: this application adopts semiconductor two-dimensional material and semiconductor to constitute two schottky barrier back to make this application have lower dark current. The semiconductor two-dimensional material is modified on the surface of the photosensitive two-dimensional material forming one Schottky junction, so that the photoelectric detector can be driven to carry out light detection without voltage.
Drawings
Fig. 1 is a schematic structural diagram of the present application.
Fig. 2 is a schematic flow chart of the present application.
Fig. 3 is a graph of current-voltage characteristics of the asymmetric double schottky junction of graphene/silicon of the present application.
The labels in the figure are: the device comprises a semiconductor substrate 1, an insulating layer 2, a photosensitive two-dimensional material layer 3, a semiconductor two-dimensional material 4 and an electrode 5.
Examples
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
As shown in fig. 1, a two-dimensional material photodetector includes a substrate and a photosensitive two-dimensional material layer 3 composed of one or more layers of photosensitive two-dimensional materials laid on the surface of the substrate, specifically, the photosensitive two-dimensional materials may be, but not limited to, graphene, MoS2, MoTe2, PtSe2, black phosphorus or Mo2C, in this application, graphene is preferably used as the photosensitive two-dimensional material layer 3, the substrate includes a semiconductor substrate 1 and an insulating layer 2 laid on one side of the semiconductor substrate 1, wherein the semiconductor may be, but not limited to, Si, Ge or GaN, the insulating layer 2 may be, but not limited to, silicon dioxide, aluminum oxide, hafnium oxide or zirconium oxide, in this application, highly doped silicon with 50nm to 300nm thick silicon dioxide on the surface is selected, two windows with the same shape, size and depth are laterally formed on the silicon dioxide layer, and the depth of the window needs to be greater than the thickness of the silicon dioxide layer, so that the highly doped silicon substrate below the silicon dioxide layer is exposed, because of the opening of the windows, the horizontal plane of the region is relatively low, a recessed area is formed, the two transverse sides of the two windows are provided with electrodes 5, the two specific electrodes 5 are respectively positioned at the two ends of the coaxial line of the two recessed areas, because of the symmetry of the two windows, the two electrodes are also positioned at the two sides of the symmetry axis of the two windows, the two electrodes 5 are both contacted with the photosensitive two-dimensional material layer 3, preferably, the two electrodes 5 are symmetrical electrodes 5, and the two electrodes 5 can be titanium and gold respectively.
As shown in fig. 1, in the present application, the exposed surface of the semiconductor substrate 1 in the window is covered by the photosensitive two-dimensional material 3, so as to form a double schottky barrier of the photosensitive two-dimensional material 3 and the semiconductor substrate 1 back to back.
As shown in fig. 1, on the basis of the above, the photosensitive two-dimensional material layer 3 on one of the recessed regions is surface-modified with a semiconductor two-dimensional material 4, and the semiconductor two-dimensional material 4 may be, but is not limited to, a quantum dot, zinc oxide, a titanium oxide nanosheet, or a titanium oxide nanowire.
According to the method, the surface of the photosensitive two-dimensional material layer 3 of one Schottky junction forming the double Schottky barrier is modified with the semiconductor two-dimensional material 4, under illumination, photo-generated carriers generated by the semiconductor two-dimensional material 4 such as quantum dots, zinc oxide, titanium oxide nano sheets or titanium oxide nano wires can be injected into the photosensitive two-dimensional material layer 3, in the application, the photosensitive two-dimensional material layer 3 takes graphene as an example, and the photo-generated carriers are injected into the graphene to change the Fermi level of the graphene, so that the potential barrier of one Schottky junction is changed, the symmetry of the double Schottky junction is broken, the symmetry of the back-to-back double Schottky barrier formed by the graphene and silicon is broken, and therefore the voltage-free driving and low-dark-current broadband light detection function can be achieved.
The back-to-back Schottky barrier is broken through, and the two electrodes 5 are connected, so that the broadband light detection function with low dark current under no voltage drive can be realized, and the current-voltage characteristic curve is shown in figure 3.
On the basis of the above, for the convenience of understanding, the present application also provides a method for manufacturing the above-mentioned photodetector, as shown in fig. 2, comprising the following steps,
s1, making back-to-back double Schottky barriers of the photosensitive two-dimensional material and the semiconductor,
a. preparing a base, wherein the base comprises a semiconductor substrate 1 and an insulating layer 2 arranged on one surface of the semiconductor substrate 1, the semiconductor substrate 1 can be Si, Ge or GaN, the insulating layer 2 can be silicon dioxide, aluminum oxide, hafnium dioxide or zirconium oxide, the application takes Si as the substrate and silicon dioxide as the insulating layer 2 as an example, specifically, preparing a highly doped silicon wafer with 50-300nm thick SiO2 on the surface, respectively cleaning the highly doped silicon wafer with acetone, ethanol and deionized water, and then blowing the highly doped silicon wafer with a nitrogen gun, wherein the thickness of the SiO2 can be 50nm, 100nm, 150nm, 200nm, 250nm or 300 nm.
b. The method comprises the steps of transversely forming two identical windows on an insulating layer 2 to expose a semiconductor substrate 1, specifically, coating a layer of photoresist with the thickness of 1-2 microns on the surface of silicon dioxide by adopting a photoetching process, exposing the silicon dioxide to be etched after photoetching development, and etching the silicon dioxide by adopting a wet etching or reactive ion beam etching method, so that two windows are formed on one surface of a substrate, which is provided with the insulating layer, to expose highly doped silicon below the silicon dioxide.
c. Removing the residual photoresist, and transferring a layer of photosensitive two-dimensional material on the surface of the substrate by wet transfer or dry transfer to enable the exposed surface of the semiconductor substrate 1 and the surface of the insulating layer to be paved with a layer of photosensitive two-dimensional material layer 3, wherein the photosensitive two-dimensional material layer 3 can be paved on part of the surface of the insulating layer to enable the photosensitive two-dimensional material layer 3 and the Si substrate to form a back-to-back double Schottky barrier, specifically, the photosensitive two-dimensional material can be graphene, MoS2, MoTe2, PtSe2, black phosphorus or Mo2C, graphene is selected in the application, and one or more layers of graphene are transferred to the surface of the Si substrate, so that the back-to-back double Schottky barrier formed by the graphene and the silicon is obtained.
S2, manufacturing electrodes 5 on the surface of the photosensitive material layer 3, enabling the electrodes 5 to be respectively located on two transverse sides of two windows and to be in contact with the photosensitive two-dimensional material layer 3, wherein the electrodes 5 can be partially arranged on an insulating layer, concretely, by adopting a photoetching process, photoresist is coated on the parts, needing to be provided with the electrodes, of the photosensitive two-dimensional material 3, photoetching and developing are carried out, two holes for evaporating a source-drain electrode 5 are formed in the photoresist, the holes are respectively located on two sides of the symmetrical axes of the two windows, the two windows are located between the holes, namely, the holes are located on two transverse sides of the double-Schottky barrier, concretely, the holes can be respectively located at two ends of the double-Schottky barrier, then, metal titanium and gold are evaporated by adopting an electron beam at the split holes, and then, residual photoresist is removed by using an acetone; the source and drain electrodes 5 are symmetrical electrodes 5, and thus a drain electrode, a window and a source electrode are formed in the transverse direction.
S3, modifying the surface of the photosensitive two-dimensional material in one of the windows constituting the double schottky barrier with a semiconductor two-dimensional material 4, specifically, performing photolithography and development, exposing one of the schottky barriers on the photoresist, and spin-coating the semiconductor two-dimensional material 4 on the exposed graphene surface, where the semiconductor two-dimensional material 4 may be a quantum dot, zinc oxide, titanium oxide nanosheet, or titanium oxide nanowire.
Finally, an asymmetric double-Schottky junction of graphene/silicon is formed on the substrate and connected with the two electrodes 5, so that the broadband light detection function with low dark current can be realized in a voltage-free driving state.
The step S3 may be performed with step S2, that is, after the schottky barrier is formed, the step S3 may be performed to perform surface modification on the photosensitive two-dimensional material layer 3, and after the surface modification is completed, the step S2 is performed.
The broadband light detection device has the advantages of being small in dark current, capable of achieving broadband light detection function of low dark current under no voltage drive after being modified with the semiconductor two-dimensional material 4, simple in structure, low in cost, high in response speed, small in dark current noise and wide in response spectrum range.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (8)

1. A manufacturing method of a two-dimensional material photodetector is characterized by comprising the following steps of S1, manufacturing back-to-back double Schottky barriers of a photosensitive two-dimensional material and a semiconductor, specifically comprising a, preparing a base, wherein the base comprises a semiconductor substrate (1) and an insulating layer (2) arranged on one surface of the semiconductor substrate (1), b, forming two symmetrical windows on the insulating layer (2) to expose the semiconductor substrate (1), c, arranging a layer of photosensitive two-dimensional material on the surface of the base, which is provided with the windows, to form a photosensitive two-dimensional material layer (3), wherein the photosensitive two-dimensional material layer (3) covers the surface of the insulating layer (2) and covers the whole surface of the exposed semiconductor substrate (1), so that the photosensitive two-dimensional material layer (3) and the semiconductor substrate (1) form back-to-back double Schottky barriers, s2, manufacturing two electrodes (5) on one surface of the photosensitive two-dimensional material layer (3) far away from the semiconductor substrate (1), enabling the two electrodes (5) to be respectively located on two sides of the symmetry axes of the two windows and enabling the two windows to be located between the two electrodes (5);
further comprising the step of surface modifying the layer of photosensitive two-dimensional material (3) in one of the windows constituting the double schottky barrier with a semiconductor two-dimensional material (4).
2. A method of manufacturing a two-dimensional material photodetector as claimed in claim 1, characterized in that said layer of photosensitive two-dimensional material (3) is graphene, MoS2, MoTe2, PtSe2, black phosphorus or Mo 2C.
3. The method for manufacturing a two-dimensional material photodetector as claimed in claim 1, characterized in that said semiconductor two-dimensional material (4) is quantum dots, zinc oxide, titanium oxide nanosheets or titanium oxide nanowires.
4. A method of fabricating a two-dimensional material photodetector as claimed in claim 1, characterized in that said semiconductor substrate (1) is Si, Ge or GaN and said insulating layer (2) is silicon dioxide, aluminum oxide, hafnium oxide or zirconium oxide.
5. A method of manufacturing a two-dimensional material photodetector as claimed in claim 1, characterized in that said electrodes (5) are symmetrical electrodes (5).
6. A two-dimensional material photodetector is characterized by comprising a base, wherein the base comprises a semiconductor substrate (1) and an insulating layer (2) arranged on one surface of the semiconductor substrate (1), two symmetrical windows are arranged on the insulating layer (2), the semiconductor substrate (1) in the windows is exposed, a photosensitive two-dimensional material layer (3) is arranged on one surface of the substrate, which is provided with the window, the photosensitive two-dimensional material layer (3) covers the surface of the insulating layer (2) and covers the whole surface of the semiconductor substrate (1) exposed in the window, two electrodes (5) are arranged on one surface, far away from the semiconductor substrate (1), of the photosensitive two-dimensional material layer (3), the two electrodes (5) are located on two sides of the symmetry axis of the two windows, and the two windows are located between the two electrodes (5); the surface of the photosensitive two-dimensional material layer (3) in one of the windows is modified with a semiconductor two-dimensional material (4).
7. A two-dimensional material photodetector according to claim 6, characterized in that said semiconducting two-dimensional material (4) is a quantum dot, zinc oxide, titanium oxide nanoplatelet or titanium oxide nanowire.
8. A two-dimensional material photodetector according to claim 6, characterized in that said layer of photosensitive two-dimensional material (3) is graphene, MoS2, MoTe2, PtSe2, black phosphorus or Mo2C, said semiconductor substrate (1) is Si, Ge or GaN and said insulating layer (2) is silicon dioxide, aluminum oxide, hafnium oxide or zirconium oxide.
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