CN113380906A - Transparent ultraviolet photoelectric detector based on metal-semiconductor-metal structure - Google Patents
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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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022491—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of a thin transparent metal layer, e.g. gold
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
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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
- H01L31/08—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
- H01L31/10—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 characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
- H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type
- H01L31/1085—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type the devices being of the Metal-Semiconductor-Metal [MSM] Schottky barrier type
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Abstract
The invention discloses a transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure, which sequentially comprises a transparent substrate, an active layer and an interdigital electrode from bottom to top; the active layer is a transparent wide-bandgap semiconductor, the forbidden band width is more than 3.1 eV, and the thickness is more than the penetration depth of ultraviolet light; the interdigital electrode is an ultrathin metal film, the thickness of the interdigital electrode is less than or equal to 15 nm, and the visible light-near infrared band transmissivity is greater than 70%; the whole ultraviolet photoelectric detector is transparent, and the transmissivity of a visible light-near infrared waveband is more than 65%. The invention has the advantages of simple structure, easy processing, high responsiveness, high response speed and good flexibility, and has great potential for being applied to the fields of transparent optoelectronic devices and flexible wearable optoelectronic devices.
Description
Technical Field
The invention belongs to the technical field of semiconductor optoelectronic devices, and particularly relates to a transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure.
Background
The transparent ultraviolet photoelectric detector is a photoelectronic device which converts an optical signal of an ultraviolet waveband into an electric signal for measurement and has a transparent appearance, can be used in the application fields of traditional non-transparent ultraviolet detectors such as an ultraviolet communication system, pollution detection and flame monitoring, and also has an irreplaceable effect in novel transparent electronic devices such as an intelligent window and an electronic skin.
The transparent ultraviolet photoelectric detector generally comprises a transparent substrate, a wide bandgap semiconductor active layer and a transparent electrode. At present, the transparent ultraviolet photoelectric detector is mainly classified according to the working principle, and comprises a photoconductive detector, a p-n junction photodiode and a schottky junction photodiode. The other type of photodetector with a simple structure, namely a photodiode with a metal-semiconductor-metal structure, has few reports in the field of transparent ultraviolet photodetectors, and the main reason is that the metal thin film electrode in the structure seriously influences the transmissivity of the device. Meanwhile, since the metal electrode forms a large-area shield on the active layer, the metal-semiconductor-metal structured photodetector generally has a problem of low responsivity.
In the prior art, the commercial transparent conductive film ITO has the characteristics of brittleness, easy breakage, rare elements and high price. Emerging carbon-based transparent electrodes, such as graphene, carbon nanotubes, organic polymers, and the like, have poor conductivity due to low carrier concentration. The metal nanowires are often randomly distributed, have large roughness, have poor adhesion with the substrate and are easy to fall off. The metal mesh structure usually needs thicker mesh lines to ensure that the metal mesh structure has sufficiently high conductivity, and at the moment, the transmissivity is limited by the size of the mesh opening rate, the surface roughness is obviously increased, and the packaging process is challenged.
Disclosure of Invention
The invention aims to overcome the disadvantages of the prior art and provides a transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure.
The purpose of the invention is realized by the following technical scheme:
a transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure comprises a transparent substrate, an active layer and an interdigital electrode from bottom to top in sequence; the active layer is a transparent wide-bandgap semiconductor, the forbidden band width is more than 3.1 eV, and the thickness is more than the penetration depth of ultraviolet light; the interdigital electrode is an ultrathin metal film, the thickness of the interdigital electrode is less than or equal to 15 nm, and the visible light-near infrared band transmissivity is greater than 70%; the whole ultraviolet photoelectric detector is transparent, and the transmissivity of a visible light-near infrared waveband is more than 65%.
The transparent substrate is made of rigid or flexible materials.
The interdigital electrode is an ultrathin metal film and adopts a single metal, metal alloy, a metal/medium double-layer structure or a medium/metal/medium three-layer structure.
The single metal is silver, gold, platinum, copper or aluminum; the metal alloy is silver-aluminum alloy, silver-copper alloy, copper-aluminum alloy or oxygen-doped silver; in the metal/medium double-layer structure or the medium/metal/medium three-layer structure, the metal is silver, gold, platinum, copper or aluminum, and the medium is zinc oxide, molybdenum oxide, aluminum oxide, tungsten oxide, vanadium oxide or ITO.
The transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure is integrated on an intelligent glass window, an intelligent mobile phone screen or a wearable device and used for sensing or monitoring ultraviolet rays.
The transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure is integrated on electronic skin and used for monitoring the dose of ultraviolet irradiation in real time.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the transparent metal film as the electrode, so that the ultraviolet photoelectric detector based on the metal-semiconductor-metal structure has transparent appearance, the transmissivity of the ultraviolet photoelectric detector in visible light-near infrared wave band is higher than that of the traditional ultraviolet photoelectric detector adopting the metal-semiconductor-metal structure prepared by the non-transparent metal film, and the ultraviolet photoelectric detector has wide application market in the field of transparent photoelectronic devices.
(2) The metal film adopted by the invention has enough high transmissivity to ultraviolet light, so that the transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure has higher photoelectric responsivity compared with the traditional non-transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure.
(3) The transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure is prepared by adopting a standard CMOS (complementary metal oxide semiconductor) process and is suitable for mass production.
(4) The transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure has high response speed and is easy to integrate.
(5) The transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure can be manufactured on a rigid substrate and a flexible substrate, so that the whole device has certain mechanical flexibility, and the whole device is transparent, so that the transparent ultraviolet photoelectric detector has a wide application market in the field of flexible wearable optoelectronic devices.
Drawings
Fig. 1 is a schematic structural view of embodiment 1 of the present invention.
Fig. 2 is an interdigital electrode region transmission spectrum of example 2 of the present invention.
FIG. 3 is a spectral response curve of example 2 of the present invention.
Fig. 4 is an optical transient response diagram of embodiment 2 of the present invention.
Fig. 5 is a graph of the optical transient response of example 3 of the present invention at different bend radii.
As shown in fig. 1, wherein 1 denotes a transparent substrate, 2 denotes an active layer, and 3 denotes an interdigital electrode.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the following embodiments and accompanying drawings. The following examples are described only to illustrate the present invention, but not to limit the scope of the present invention.
Example 1
As shown in fig. 1, a transparent ultraviolet photodetector based on a metal-semiconductor-metal structure includes a transparent substrate 1, an active layer 2 and an interdigital electrode 3, which are sequentially distributed from bottom to top.
The active layer 2 is a transparent wide-bandgap semiconductor, the forbidden band width is more than 3.1 eV, and the thickness is more than the penetration depth of ultraviolet light; the interdigital electrode 3 is an ultrathin metal film, the thickness of the interdigital electrode is less than or equal to 15 nm, and the visible light-near infrared band transmissivity is greater than 70%; the whole ultraviolet photoelectric detector is transparent, and the transmissivity of a visible light-near infrared waveband is more than 65%.
The transparent substrate 1 is made of rigid or flexible material.
The interdigital electrode 3 is an ultrathin metal film and adopts a single metal, metal alloy, a metal/medium double-layer structure or a medium/metal/medium three-layer structure.
The single metal is silver, gold, platinum, copper or aluminum; the metal alloy is silver-aluminum alloy, silver-copper alloy, copper-aluminum alloy or oxygen-doped silver; in the metal/medium double-layer structure or the medium/metal/medium three-layer structure, the metal is silver, gold, platinum, copper or aluminum, and the medium is zinc oxide, molybdenum oxide, aluminum oxide, tungsten oxide, vanadium oxide or ITO.
Ultraviolet light enters the active layer through the top interdigital electrode region, generates light after being absorbed to generate electrons and holes, and is collected by the interdigital electrodes under the action of built-in potential and/or external bias voltage, so that photocurrent is formed. Because the top interdigital electrode has certain transmissivity to ultraviolet light, the shielding effect of the top interdigital electrode on the ultraviolet light can be obviously reduced, and the photocurrent is increased, so that the device has higher photoelectric responsivity compared with the traditional non-transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure. If the transparent substrate is made of rigid materials or flexible materials, the transparent ultraviolet photoelectric detector can be integrated in transparent optoelectronic devices such as an intelligent glass window and an intelligent mobile phone screen and is used for monitoring ultraviolet rays; if the proximity sensor in the mobile phone screen sends an ultraviolet signal for sensing, the transparent ultraviolet photoelectric detector can also help the smart phone to eliminate the bang. In particular, if the transparent substrate is made of a flexible material, the transparent ultraviolet photodetector has good mechanical flexibility, can be attached to any surface, and has a wider application range, for example, the transparent ultraviolet photodetector can be integrated on electronic skin and used in the field of wearable devices.
Example 2
The transparent ultraviolet photodetector based on the metal-semiconductor-metal structure shown in this embodiment is prepared by the following method: quartz glass is selected as a transparent substrate, and zinc oxide with the thickness of 480 nm is sputtered and deposited on the transparent substrate to be used as an active layer; and finally, preparing an ultrathin silver film with the thickness of 7 nm by taking the photoresist as a mask and adopting sputtering and stripping processes to serve as an interdigital electrode. For comparison, a non-transparent ultraviolet photodetector with a 50 nm thick silver film as an interdigital electrode was also prepared using the above method. The width of the interdigital electrode is 2.5 μm and the interval is 4 μm. In the embodiment, the active layer zinc oxide film also plays a role of a seed layer, surface energy is regulated and controlled, and a continuous film is formed when the thickness of the silver film is only 7 nm. In the prior art, a metal film with the thickness of less than 15 nm is usually prepared by adopting a physical vapor deposition process, but is influenced by a three-dimensional Volmer-Weber growth mode, a continuous film is difficult to form, and the transparency and the conductivity of the film are low, so that a transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure is not developed by other people by adopting an ultrathin metal film.
Fig. 2 shows the transmission spectrum of the ultraviolet photoelectric detector based on the metal-semiconductor-metal structure with the silver electrode thickness of 7 nm and 50 nm in the interdigital electrode area. Compared with a silver film electrode with the thickness of 50 nm, the ultrathin silver film transparent electrode with the thickness of 7 nm obviously improves the transmissivity of an interdigital electrode area in visible light and near infrared bands, and the average transmissivity is improved from 50% to 80%.
Fig. 3 shows spectral response curves of the uv photodetector based on the metal-semiconductor-metal structure with silver film thicknesses of 7 nm and 50 nm, respectively. As can be seen from fig. 3, the responsivity of the two detectors to the optical signal in the ultraviolet band is much higher than that to the optical signal in the visible band, and the rejection ratio is high; the responsivity of the ultraviolet photoelectric detector adopting the ultrathin silver film transparent electrode with the thickness of 7 nm to an ultraviolet signal is higher than that of the non-transparent ultraviolet photoelectric detector adopting the silver film electrode with the thickness of 50 nm, which shows that the responsivity of the ultraviolet photoelectric detector based on a metal-semiconductor-metal structure is remarkably improved by the transparent electrode.
FIG. 4 shows the optical transient response of a UV photodetector based on a metal-semiconductor-metal structure with silver film thicknesses of 7 nm and 50 nm, respectively, at a test light source wavelength of 370 nm and a power density of 0.3 mW/cm2. As can be seen from fig. 4, both of the above detectors produced a fast, stable, repeatable photo-response, in which the photocurrent of the metal-semiconductor-metal structure-based transparent uv photodetector using the ultra-thin silver film transparent electrode of 7 nm thickness was greater.
Example 3
The transparent ultraviolet photodetector based on the metal-semiconductor-metal structure shown in this embodiment uses PET as a flexible transparent substrate, 480 nm thick zinc oxide as an active layer, and 7 nm thick ultra-thin silver film as a transparent interdigital electrode, and the interdigital electrode structure and the preparation steps are the same as those of embodiment 2.
Fig. 5 shows the optical transient response of the flexible transparent uv photodetector prepared in this embodiment under different bending radii. As can be seen from fig. 5, when the bending radius is greater than or equal to 7 mm, the flexible transparent ultraviolet photodetector described in this embodiment can produce a fast, stable, repeatable response, and has good mechanical flexibility.
Example 4
The present embodiment applies the flexible transparent ultraviolet photodetector shown in embodiment 3 to a wearable device. Proper amount of ultraviolet radiation can promote the synthesis of vitamin D, and excessive amount of ultraviolet radiation can cause skin cancer and other diseases. The flexible transparent ultraviolet photodetector shown in example 3 was integrated into electronic skin for real-time monitoring of the dose of ultraviolet radiation, and health guidance was given after statistics and analysis. The ultraviolet photoelectric detector shown in the embodiment has transparent appearance, and the appearance is not influenced by integration on electronic skin; in addition, the ultraviolet photoelectric detector shown in the embodiment has good flexibility, so that the ultraviolet photoelectric detector can be comfortably worn and used for a long time.
The embodiments in the above description can be further combined or replaced, and the embodiments are only described as preferred embodiments of the present invention, and do not limit the concept and scope of the present invention, and various changes and modifications made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention belong to the protection scope of the present invention. The scope of the invention is given by the appended claims and any equivalents thereof.
Claims (6)
1. A transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure is characterized in that a transparent substrate, an active layer and an interdigital electrode are sequentially arranged from bottom to top; the active layer is a transparent wide-bandgap semiconductor, the forbidden band width is more than 3.1 eV, and the thickness is more than the penetration depth of ultraviolet light; the interdigital electrode is an ultrathin metal film, the thickness of the interdigital electrode is less than or equal to 15 nm, and the visible light-near infrared band transmissivity is greater than 70%; the whole ultraviolet photoelectric detector is transparent, and the transmissivity of a visible light-near infrared waveband is more than 65%.
2. The metal-semiconductor-metal structure based transparent ultraviolet photodetector of claim 1, wherein the transparent substrate is made of rigid or flexible material.
3. The metal-semiconductor-metal structure-based transparent ultraviolet photodetector as claimed in claim 1, wherein the interdigital electrode is an ultra-thin metal film, and adopts a single metal, a metal alloy, a metal/medium double-layer structure or a medium/metal/medium triple-layer structure.
4. The metal-semiconductor-metal structure based transparent uv photodetector of claim 3, wherein said single metal is silver, gold, platinum, copper or aluminum; the metal alloy is silver-aluminum alloy, silver-copper alloy, copper-aluminum alloy or oxygen-doped silver; in the metal/medium double-layer structure or the medium/metal/medium three-layer structure, the metal is silver, gold, platinum, copper or aluminum, and the medium is zinc oxide, molybdenum oxide, aluminum oxide, tungsten oxide, vanadium oxide or ITO.
5. The metal-semiconductor-metal structure based transparent ultraviolet photodetector of claim 1, integrated in a smart glazing, a smart phone screen or a wearable device for sensing or ultraviolet monitoring.
6. The metal-semiconductor-metal structure based transparent ultraviolet photodetector according to claim 1 or 5, characterized in that it is integrated in the electronic skin for real-time monitoring of the dose of ultraviolet radiation.
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