CN110335900B - Indium tin oxide/vertical graphene photoelectric detector composite structure and preparation method thereof - Google Patents
Indium tin oxide/vertical graphene photoelectric detector composite structure and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 113
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 title claims abstract description 58
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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
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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
- H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
An indium tin oxide/vertical graphene photoelectric detector composite structure and a preparation method thereof belong to the technical field of photoelectric detectors. The structure of the photoelectric detector is sequentially from bottom to top: glass as a substrate of the device; the vertical graphene is used as a light absorption layer and an electron transmission layer of the device; the indium tin oxide film is used as a transparent current auxiliary diffusion layer; and titanium/gold electrodes are arranged on two sides of the vertical graphene and are connected with an external power supply. Because the vertical graphene has a wide spectral response characteristic, the working waveband of the detector ranges from visible light to infrared waveband, the indium tin oxide thin film layer designed by the invention can effectively transmit photon-generated carriers, inhibit defect influence and improve the output photocurrent of the device. In addition, the detector has higher light absorptivity and light responsivity, can work under lower bias voltage, has simple and repeatable process preparation, and effectively improves the detection efficiency and the yield of the detector.
Description
Technical Field
The invention belongs to the structural design and the preparation method of a photoelectric detector made of a novel material, and particularly relates to a composite structural design and a preparation method of an indium tin oxide/vertical graphene photoelectric detector.
Background
The photoelectric detector is a device for converting optical signals into electric signals, and the optical detection and the photoelectric detector have important significance in modern society, from imaging, safety monitoring of communication equipment and various sensors, and display technology to basic scientific application, such as observation of universe. In general, an electronic transition should have at least two energy levels, and only incident photons with energies greater than the energy difference between the two energy levels will be absorbed. Thus, for example, InGaAs-based infrared detectors and silicon-based photodetectors, these semiconductor photodetectors have a limited detection wavelength range. However, the zero band gap structural feature of graphene enables the graphene to absorb light in a wide range of wavelengths, including ultraviolet light, visible light, infrared light and even terahertz, without the wavelength limitation of conventional detectors. The ultrahigh carrier mobility of graphene also enables the response speed of the graphene-based photodetector to be fast. Therefore, extensive research on graphene detectors has been conducted both theoretically and experimentally. However, the photoresponse rate of the current graphene photoelectric detector is at a level of several mA/W, and the main reason of low responsivity is as follows: the weak light absorption of single-layer graphene, while the carrier lifetime is in the order of ps.
Vertical graphene is a two-dimensional carbon nanostructure formed by standing multi-layer graphene on a substrate, the height and width of each independent vertical graphene sheet are adjustable from 10 nanometers to tens of micrometers, but the thickness is only a few nanometers and even less than 1nm, each graphene sheet contains 1 to 10 layers of graphene, and each layer is 0.34nm to 0.37nm apart. Vertically oriented graphene is essentially graphene, but it also has unique structural features. Thus, vertical graphene not only has the properties of graphene, but also has some unique characteristics caused by the alignment. In addition to the general properties of graphene, vertically oriented graphene has several unique properties that make them significantly different from conventional graphene thin films in many respects. Vertically oriented graphene has a unique orientation, a non-stacked morphology, and a large specific surface area, and due to these unusual properties, it possesses many unique mechanical, chemical, electronic, electrochemical, and optoelectronic properties that may serve its potential uses in a wide range of applications.
Disclosure of Invention
Because the vertical graphene has unique photoelectric characteristics and the indium tin oxide film has good light transmission and charge transmission performance, the invention provides a novel vertical graphene photoelectric detector and a preparation method of the detector. The photodetector has high light absorptivity and light responsivity.
The vertical graphene of the device is a two-dimensional carbon nano structure formed by standing multilayer graphene on a substrate, and has a high specific surface area. The vertical graphene is used as a light absorption layer of the detector, so that the detection surface area is maximized, the detection area of the device is greatly increased, and the light absorption of the detector is further increased.
The invention discloses an indium tin oxide/vertical graphene photoelectric detector which is characterized by sequentially comprising the following structures from bottom to top: glass as a substrate of the device; vertical graphene on a substrate serves as a light absorption layer and an electron transport layer of the device; an indium tin oxide film on the vertical graphene is used as a transparent current auxiliary diffusion layer; and titanium/gold electrodes are arranged on two sides of the vertical graphene and are connected with an external power supply.
The vertical graphene of the device is composed of a horizontal buffer layer in contact with a substrate and a graphene sheet array vertically grown on the buffer layer. If the vertical graphene is used as the light absorption layer of the detector alone, the light source irradiates the surface of the vertical graphene, the graphene sheet absorbs light energy to generate non-equilibrium carriers, and the carriers flow through the buffer layer when flowing to the corresponding electrode. The buffer layer is composed mainly of amorphous carbon or carbide and has a thickness lower than the height of the graphene platelet array. The amorphous carbon has more defects and larger resistance, and influences the transport of current carriers, so that the response speed of the detector is increased, and the detection performance is reduced.
The device has a thin film of indium tin oxide deposited on the vertical graphene channel. The indium tin oxide film has physical properties such as high conductivity, high transmittance and corrosion resistance. The indium tin oxide film is used as a transparent current diffusion layer of the detector, when a light source irradiates the detector, a vertical graphene channel can generate a photon-generated carrier, the photon-generated carrier enters the indium tin oxide film through the vertical graphene, the indium tin oxide film has lower resistance, the transmission resistance of the photon-generated carrier is remarkably reduced, the indium tin oxide film can be used as a transmission channel of a quick carrier, the movement speed of the carrier is increased, the carrier can reach a corresponding electrode more quickly, namely, the service life of the photon-generated carrier is prolonged, and therefore the detector can generate more photocurrent and has higher light responsivity.
According to the composite structure design and the preparation method of the indium tin oxide/vertical graphene photoelectric detector, the structure of the photoelectric detector is as follows from bottom to top in sequence: glass as a substrate of the device; the vertical graphene is used as a light absorption layer and an electron transmission layer of the device; indium tin oxide film as transparent current diffusion layer; and titanium/gold electrodes are arranged on two sides of the vertical graphene and are connected with an external power supply.
The glass substrate of the invention is common glass or soda-lime glass, quartz glass, sapphire glass and the like.
The vertical graphene is directly grown on the glass substrate, namely, a horizontal buffer layer of the vertical graphene and the substrate are grown on the substrate in parallel.
The indium tin oxide film is deposited by a magnetron sputtering technology, has a transparent conductive characteristic, and is preferably 100nm thick.
The titanium/gold electrode is deposited by a magnetron sputtering technology, and the thicknesses of the titanium layer and the gold layer in the electrode are preferably 15nm and 120nm respectively.
The preparation method of the indium tin oxide/vertical graphene photoelectric detector composite structure comprises the following steps:
(1) directly growing vertical graphene on a substrate, cleaning a vertical graphene sample: cleaning a vertical graphene sample by sequentially using an acetone solution, an ethanol solution and deionized water;
(2) preparing an indium tin oxide film: depositing an indium tin oxide film on vertical graphene growing on a glass substrate by using a magnetron sputtering technology, wherein the deposition temperature is 100 ℃;
(3) etching an indium tin oxide film channel: using AZ5214 photoresist, adopting positive photoresist photoetching technology to develop an exposed part, using the photoresist as a mask, and carrying out wet etching on the exposed part by using dilute hydrochloric acid to etch off redundant indium tin oxide;
(4) etching a vertical graphene channel on the indium tin oxide thin film channel: removing redundant vertical graphene by adopting a dry etching mode, wherein etching gas is oxygen;
(5) preparing a titanium/gold electrode: and using AZ5214 photoresist and adopting an inverse photoresist photoetching process to prepare a titanium/gold electrode in the channel.
The indium tin oxide/vertical graphene photoelectric detector composite structure is improved on the basis of a common photoconductive photoelectric detector structure. The photoconductive type photoelectric detector consists of a finite-length semiconductor layer and ohmic contacts at two ends, a fixed bias voltage is applied between the two ohmic contacts, so that a bias current flows through the semiconductor layer, and when the semiconductor absorption layer of the device is irradiated, a photocurrent is added to the bias current under the action of an external electric field, so that the conductivity of the device is effectively increased. The invention has the advantages of a photoconductive detector, such as high light responsivity, wide spectral response, good compatibility with the existing microelectronic devices and circuits, and the like. The vertical graphene is used as the light absorption layer of the detector, so that the detection area of the device is increased, and the light absorption of the detector is increased. The indium tin oxide film is used as a transparent current diffusion layer of the detector, so that the transmission resistance of photon-generated carriers is reduced, and more photocurrent is generated. In addition, the detector can work under a lower bias voltage, the process preparation is simple and repeatable, and a foundation is laid for the research of the vertical graphene photoelectric detector. The detector has high light absorptivity and light responsivity, can work under low bias voltage, is simple and repeatable in process preparation, and effectively improves the detection efficiency and the yield of the detector.
Drawings
FIG. 1 is a schematic diagram of a three-dimensional structure of an ITO/vertical graphene photodetector composite structure according to the present invention;
in the figure: 1.1-glass substrate, 1.2-vertical graphene channel, 1.3-indium tin oxide film and 1.4-titanium/gold electrode.
FIG. 2 is a flow chart of the fabrication of the ITO/vertical graphene photodetector composite structure of the present invention;
in the figure: 2.1-cleaning a vertical graphene sample, 2.2-preparing an indium tin oxide film, 2.3-etching an indium tin oxide film channel, 2.4-etching a vertical graphene channel, and 2.5-preparing a titanium/gold electrode.
Fig. 3 is a graph showing the photocurrent test results of the vertical graphene photodetector (with an indium tin oxide film) and the vertical graphene photodetector (without an indium tin oxide film) according to the present invention.
Detailed Description
Referring to fig. 1, the indium tin oxide/vertical graphene photoelectric detector composite structure of the invention comprises, from bottom to top, a 1.1-glass substrate, a 1.2-vertical graphene channel, a 1.3-indium tin oxide film, and a 1.4-titanium/gold electrode.
Wherein, the glass substrate of the invention is common glass or soda-lime glass.
The vertical graphene of the invention is grown on a glass substrate.
The indium tin oxide film is deposited by a magnetron sputtering technology, and the thickness of the indium tin oxide film is 100 nm.
The titanium/gold electrode is deposited by a magnetron sputtering technology, and the thicknesses of the titanium layer and the gold layer in the electrode are 15nm and 120nm respectively.
Vertical graphene is a two-dimensional carbon nanostructure formed by standing multi-layer graphene on a substrate, the height and width of each independent vertical graphene sheet are adjustable from 10 nanometers to tens of micrometers, but the thickness is only a few nanometers and even less than 1nm, each graphene sheet contains 1 to 10 layers of graphene, and each layer is 0.34nm to 0.37nm apart.
The following are examples of the present invention, which are further illustrative, but not limiting, of the present invention.
Example 1: preparation method of indium tin oxide/vertical graphene photoelectric detector composite structure
The preparation method of the composite structure of the indium tin oxide/vertical graphene photoelectric detector comprises the following steps:
(1) directly growing vertical graphene on a glass substrate, wherein the height of the vertical graphene is about 400nm (the height of a buffer layer is far lower than the height of a graphene sheet, generally about 50 nm), cleaning a vertical graphene sample: cleaning a vertical graphene sample by sequentially using an acetone solution, an ethanol solution and deionized water;
(2) preparing an indium tin oxide film: depositing a 100nm indium tin oxide film on vertical graphene growing on a glass substrate by using a magnetron sputtering technology, wherein the deposition temperature is 100 ℃;
(3) etching an indium tin oxide film channel: using AZ5214 photoresist, adopting positive photoresist photoetching technology to develop an exposed part, using the photoresist as a mask, and carrying out wet etching on the exposed part by using dilute hydrochloric acid to etch off redundant indium tin oxide;
(4) etching the vertical graphene channel: removing redundant vertical graphene by adopting a dry etching mode, wherein etching gas is oxygen;
(5) preparing a titanium/gold electrode: and (3) using AZ5214 photoresist, and preparing a titanium/gold electrode by adopting an inverse photoresist photoetching process, wherein the thicknesses of a titanium layer and a gold layer in the electrode are 15nm and 120nm respectively.
(6) The completed device is shown in fig. 1.
Example 2: photocurrent testing of a vertical graphene photodetector (no indium tin oxide film) (i.e., comparative example)
A vertical graphene photodetector (no indium tin oxide thin film), the device structure comprising: glass as a substrate of the device; the vertical graphene is used as a light absorption layer and an electron transmission layer of the device; and titanium/gold electrodes are arranged on two sides of the vertical graphene and are connected with an external power supply. Referring to the circular curve (●) in fig. 3, the test is performed at room temperature and standard atmospheric pressure, a 980nm semiconductor pump laser is used as a test light source, the light power of the light source is 239 μ W, and under the external bias voltage of 0.1V, the photocurrent generated by the detector is 3.02 μ a, and the light responsivity is 12.6 mA/W.
Example 3: photocurrent testing of vertical graphene photodetectors (with indium tin oxide films)
A vertical graphene photodetector (with indium tin oxide thin film), the device structure comprising: glass as a substrate of the device; the vertical graphene is used as a light absorption layer and an electron transmission layer of the device; indium tin oxide film as transparent current diffusion layer; and titanium/gold electrodes are arranged on two sides of the vertical graphene and are connected with an external power supply. Referring to a triangle (T-shaped) curve in FIG. 3, the test is performed at room temperature and standard atmospheric pressure, a 980nm semiconductor pump laser is used as a test light source, the light power of the light source is 239 μ W, the photocurrent generated by the detector is 13.4 μ A and the light responsivity is 56.1mA/W under an external bias voltage of 0.1V.
According to the experimental results of the embodiments 2 and 3, it is shown that the photocurrent generated by the vertical graphene photodetector with the ito film is about 4 times that of the vertical graphene photodetector without the ito film, which indicates that the photodetector structure of the present invention can effectively generate more photocurrent and increase the photoresponse of the device.
The above is a detailed introduction of the composite structure of the ito/vertical graphene photodetector of the present invention, and the basic structure, the preparation method and the embodiments of the present invention are described, and the above examples are provided to help explain the basic idea of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention, and these modifications are within the scope of the appended claims.
Claims (7)
1. The utility model provides an indium tin oxide/perpendicular graphite alkene photoelectric detector which its structure from supreme is in proper order down: glass as a substrate of the device; vertical graphene on a substrate serves as a light absorption layer and an electron transport layer of the device; an indium tin oxide film on the vertical graphene is used as a transparent current auxiliary diffusion layer; and titanium/gold electrodes are arranged on two sides of the vertical graphene and are connected with an external power supply.
2. An indium tin oxide/vertical graphene photodetector as claimed in claim 1, wherein the glass substrate is soda lime glass, quartz glass or sapphire glass.
3. An ito/vertical graphene photodetector according to claim 1, wherein the vertical graphene is grown directly on the glass substrate, i.e. the horizontal buffer layer of vertical graphene is grown on the substrate parallel to the substrate.
4. An indium tin oxide/vertical graphene photodetector as claimed in claim 1, wherein the indium tin oxide film has a transparent conductive property.
5. An indium tin oxide/vertical graphene photodetector as claimed in claim 1, wherein the indium tin oxide thin film has a thickness of 100 nm.
6. An indium tin oxide/vertical graphene photodetector as claimed in claim 1, wherein the thickness of the titanium layer and the thickness of the gold layer in the titanium/gold electrode are 15nm and 120nm, respectively.
7. The method of fabricating an indium tin oxide/vertical graphene photodetector of any one of claims 1 to 6, comprising the steps of:
(1) directly growing vertical graphene on a substrate, cleaning a vertical graphene sample: cleaning a vertical graphene sample by sequentially using an acetone solution, an ethanol solution and deionized water;
(2) preparing an indium tin oxide film: depositing an indium tin oxide film on vertical graphene growing on a glass substrate by using a magnetron sputtering technology, wherein the deposition temperature is 100 ℃;
(3) etching an indium tin oxide film channel: using AZ5214 photoresist, adopting positive photoresist photoetching technology to develop an exposed part, using the photoresist as a mask, and carrying out wet etching on the exposed part by using dilute hydrochloric acid to etch off redundant indium tin oxide;
(4) etching a vertical graphene channel on the indium tin oxide thin film channel: removing redundant vertical graphene by adopting a dry etching mode, wherein etching gas is oxygen;
(5) preparing a titanium/gold electrode: and using AZ5214 photoresist and adopting an inverse photoresist photoetching process to prepare a titanium/gold electrode in the channel.
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