CN113380906B - Transparent ultraviolet photoelectric detector based on metal-semiconductor-metal structure - Google Patents
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Classifications
-
- 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
-
- 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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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
- Light Receiving Elements (AREA)
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 interdigital electrodes from bottom to top; the active layer is a transparent wide forbidden band semiconductor, the forbidden band width is larger than 3.1 and eV, and the thickness is larger than the ultraviolet penetration depth; the interdigital electrode is an ultrathin metal film, the thickness is less than or equal to 15 nm, and the visible light-near infrared band transmittance is more than 70%; the whole ultraviolet photoelectric detector is transparent, and the transmittance of visible light-near infrared wave band is more than 65%. The invention has the advantages of simple structure, easy processing, high response speed, good flexibility and 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 an optoelectronic device which converts an optical signal of an ultraviolet band into an electric signal for measurement and has a transparent appearance, can be used for the application fields of traditional non-transparent ultraviolet detectors such as an ultraviolet communication system, pollution detection, flame monitoring and the like, and has an irreplaceable function in novel transparent electronic devices such as intelligent windows, electronic skins and the like.
The transparent ultraviolet photoelectric detector generally comprises a transparent substrate, a wide bandgap semiconductor active layer and a transparent electrode. Currently, transparent ultraviolet photodetectors are classified according to the working principle, and mainly include three types of photoconductive detectors, p-n junction photodiodes and schottky junction photodiodes. Another photodiode with a simple structure, namely a metal-semiconductor-metal structure, has not been reported in the field of transparent ultraviolet photodetectors, mainly because the transmittance of the device is seriously affected by a metal thin film electrode in the structure. Meanwhile, since the metal electrode forms a large-area shielding 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 brittle property, is easy to break, contains rare elements and has 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 distributed randomly, have large roughness, poor adhesion with the substrate and are easy to fall off. The metal grid structure often needs thicker grid lines to ensure that the metal grid structure has high enough conductivity, and at the moment, the transmissivity is limited by the size of the grid aperture ratio, 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 aim of the invention is achieved 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 interdigital electrodes from bottom to top in sequence; the active layer is a transparent wide forbidden band semiconductor, the forbidden band width is larger than 3.1 and eV, and the thickness is larger than the ultraviolet penetration depth; the interdigital electrode is an ultrathin metal film, the thickness is less than or equal to 15 nm, and the visible light-near infrared band transmittance is more than 70%; the whole ultraviolet photoelectric detector is transparent, and the transmittance of visible light-near infrared wave band 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, metal/medium double-layer structure or 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 in an intelligent glass window, a smart phone screen or a wearable device and is used for sensing or monitoring ultraviolet rays.
The transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure is integrated on the electronic skin and is 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, has higher transmissivity in visible light-near infrared wave bands than the traditional ultraviolet photoelectric detector with the metal-semiconductor-metal structure prepared by adopting the non-transparent metal film, and has wide application market in the field of transparent photoelectronic devices.
(2) The metal film adopted by the invention has high enough transmissivity to ultraviolet light, so the transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure has higher photoelectric response 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, is transparent, and has 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 a transmission spectrum of the interdigital electrode region of example 2 of the present invention.
FIG. 3 is a spectral response curve of example 2 of the present invention.
Fig. 4 is a graph of the optical transient response 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 scheme of the present invention will be described in detail and clearly with reference to the following examples and the accompanying drawings. The examples described below are only for illustration of the invention, but are not intended to limit the scope of the invention.
Example 1
As shown in fig. 1, a transparent ultraviolet photodetector based on a metal-semiconductor-metal structure comprises a transparent substrate 1, an active layer 2 and interdigital electrodes 3 which are sequentially distributed from bottom to top.
The active layer 2 is a transparent wide forbidden band semiconductor, the forbidden band width is larger than 3.1 and eV, and the thickness is larger than the ultraviolet penetration depth; the interdigital electrode 3 is an ultrathin metal film, the thickness is less than or equal to 15 nm, and the visible light-near infrared band transmittance is more than 70%; the whole ultraviolet photoelectric detector is transparent, and the transmittance of visible light-near infrared wave band is more than 65%.
The transparent substrate 1 is made of a rigid or flexible material.
The interdigital electrode 3 is an ultrathin metal film and adopts a single metal, metal alloy, metal/medium double-layer structure or 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, and is absorbed to generate photo-generated electrons and holes, which are collected by the interdigital electrode under the action of built-in potential and/or external bias voltage, thereby forming photocurrent. Because the top interdigital electrode has certain transmissivity to ultraviolet light, the shielding effect to ultraviolet light can be obviously reduced, and thus, 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 material or flexible material, the transparent ultraviolet photoelectric detector can be integrated in transparent optoelectronic devices such as intelligent glass windows, intelligent mobile phone screens and the like and is used for monitoring ultraviolet rays; if the proximity sensor in the mobile phone screen sends out an ultraviolet signal for sensing, the transparent ultraviolet photoelectric detector can also help the smart phone to eliminate the bang. Particularly, if the transparent substrate is made of flexible materials, the transparent ultraviolet photoelectric detector has good mechanical flexibility, can be attached to any surface, has wider application fields, can be integrated on electronic skin, and is used in the field of wearable devices.
Example 2
The transparent ultraviolet photoelectric detector based on the metal-semiconductor-metal structure shown in the embodiment is prepared by the following method: selecting quartz glass as a transparent substrate, and sputtering and depositing zinc oxide with the thickness of 480 nm on the transparent substrate to serve as an active layer; finally, using photoresist as a mask, and adopting sputtering and stripping processes to prepare an ultrathin silver film with the thickness of 7 nm as an interdigital electrode. For comparison, a non-transparent uv photodetector with 50 nm thick silver film as an interdigital electrode was also prepared using the above method. The width of the interdigital electrodes was 2.5 μm, and the interval was 4. Mu.m. In this embodiment, the active layer zinc oxide film also plays a role of a seed layer, and regulates and controls the surface energy, so that the silver film forms a continuous film when the thickness is only 7 nm a. In the prior art, a metal film with the thickness smaller than 15 and nm is often 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 continuous film are low, so that no other people have developed a transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure by adopting an ultrathin metal film.
Fig. 2 shows the transmission spectra of uv photodetectors based on metal-semiconductor-metal structures with silver electrode thicknesses of 7 nm and 50 nm, respectively, in the interdigital electrode areas. Compared with a silver film electrode with the thickness of 50 nm, the ultra-thin silver film transparent electrode with the thickness of 7 nm remarkably improves the transmittance of the interdigital electrode region in visible light and near infrared bands, and the average transmittance is improved from 50% to 80%.
Fig. 3 shows the spectral response curves of uv photodetectors based on metal-semiconductor-metal structures with silver film thicknesses of 7 nm and 50 nm, respectively. As can be seen from fig. 3, the responsivity of the above two detectors to ultraviolet band light signals is far higher than that of the detectors to visible band light signals, and the inhibition ratio is high; the ultraviolet photoelectric detector adopting the 7 nm thick ultrathin silver film transparent electrode has higher responsivity to ultraviolet signals than the non-transparent ultraviolet photoelectric detector adopting the 50 nm thick silver film electrode, which proves that the transparent electrode obviously improves the responsivity of the ultraviolet photoelectric detector based on the metal-semiconductor-metal structure.
FIG. 4 shows the light transient response of UV photodetectors based on metal-semiconductor-metal structures with silver film thicknesses of 7 nm and 50 nm, respectively, with a test light source wavelength of 370 nm and a power density of 0.3 mW/cm 2 . As can be seen from fig. 4, both of the above-described detectors produced a fast, stable, repeatable photo-response in which the photocurrent of the metal-semiconductor-metal structure based transparent uv photodetector using a 7 nm thick ultra-thin silver film transparent electrode was greater.
Example 3
The transparent uv photodetector based on metal-semiconductor-metal structure shown in this example 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 example 2.
Fig. 5 shows the optical transient response of the flexible transparent uv photodetector prepared in this example at different bending radii. As can be seen from fig. 5, when the bending radius is equal to or greater than 7 mm, the flexible transparent uv photodetector according to this embodiment can generate a rapid, stable and repeatable response, and has good mechanical flexibility.
Example 4
This embodiment applies the flexible transparent uv photodetector illustrated in embodiment 3 to a wearable device. The vitamin D synthesis can be promoted by receiving a proper amount of ultraviolet radiation, and skin cancer and other diseases can be caused by excessive ultraviolet radiation. 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 after statistics and analysis, health guidance was given. The ultraviolet photoelectric detector shown in the embodiment has transparent appearance, and the integration of the ultraviolet photoelectric detector in the electronic skin does not affect the beauty; in addition, the ultraviolet photoelectric detector shown in the embodiment has good flexibility, so that the ultraviolet photoelectric detector can be worn comfortably and used for a long time.
The embodiments in the foregoing description may be further combined or replaced, and the embodiments are merely illustrative of the preferred embodiments of the present invention and are not intended to limit the spirit and scope of the present invention, and various changes and modifications made by those skilled in the art to which the present invention pertains without departing from the spirit of the present invention. The scope of the invention is given by the appended claims and any equivalents thereof.
Claims (3)
1. A transparent ultraviolet photoelectric detector based on a metal-semiconductor-metal structure is characterized by sequentially comprising a transparent substrate, an active layer and interdigital electrodes from bottom to top; the active layer is transparent wide-bandgap semiconductor zinc oxide, the forbidden bandwidth is larger than 3.1 and eV, and the thickness is larger than the ultraviolet penetration depth; the interdigital electrode is an ultrathin silver film, the thickness is 7 nm, the transmissivity of visible light-near infrared wave band is more than 70%, and the interdigital electrode has high transmissivity to ultraviolet light; the whole ultraviolet photoelectric detector is transparent, the transmissivity of visible light-near infrared wave band is more than 65%, and the ultraviolet photoelectric detector has high photoelectric responsivity;
the transparent substrate is made of flexible materials, and the bending radius of the whole ultraviolet photoelectric detector is as small as 7-10 mm.
2. The metal-semiconductor-metal structure based transparent uv photodetector of claim 1, integrated into a smart glass window, smart phone screen or wearable device for sensing or uv monitoring.
3. The metal-semiconductor-metal structure based transparent uv photodetector according to claim 1 or 2, integrated in the electronic skin for real-time monitoring of the dose of uv radiation received.
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| CN201060051Y (en) * | 2007-04-30 | 2008-05-14 | 西安交通大学 | Ultraviolet light conductance seeker of ZnO MSM structure |
| CN100468787C (en) * | 2007-04-30 | 2009-03-11 | 西安交通大学 | A making method for high-performance ZnO MSM ultra-violet photoconduction detector |
| CN101807619B (en) * | 2010-03-19 | 2012-02-01 | 河南大学 | Transparent flexible ultraviolet detector and preparation method thereof |
| CN102694052B (en) * | 2011-03-22 | 2016-01-06 | 中国科学院微电子研究所 | Semiconductor device and method for manufacturing the same |
| CN102496648A (en) * | 2011-11-28 | 2012-06-13 | 南京大学 | Ultraviolet light single-photon detector with built-in negative feedback metal-semiconductor-metal structure |
| CN103022217A (en) * | 2012-11-22 | 2013-04-03 | 中山大学 | BeMgZnO-based MSM solar blind detector and preparation method thereof |
| CN107134503A (en) * | 2017-05-04 | 2017-09-05 | 福建农林大学 | Flexible zinc oxide UV photodetector of a kind of cellulose base and preparation method thereof |
| CN108666395A (en) * | 2018-05-24 | 2018-10-16 | 北京邮电大学 | Solar blind UV electric explorer and preparation method thereof based on amorphous oxide gallium film |
| CN109449219A (en) * | 2018-09-19 | 2019-03-08 | 北京镓族科技有限公司 | Based on β-Ga2O3The solar blind ultraviolet detector of monocrystalline grade thin slice |
| CN110444618B (en) * | 2019-08-09 | 2021-10-22 | 南京大学 | Solar blind ultraviolet detector based on amorphous gallium oxide film and preparation method thereof |
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