CN114695580A - Self-bias photoelectric detector and preparation method and application thereof - Google Patents

Self-bias photoelectric detector and preparation method and application thereof Download PDF

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CN114695580A
CN114695580A CN202210256024.8A CN202210256024A CN114695580A CN 114695580 A CN114695580 A CN 114695580A CN 202210256024 A CN202210256024 A CN 202210256024A CN 114695580 A CN114695580 A CN 114695580A
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self
semiconductor layer
photodetector
bias
titanium dioxide
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潘锋
梁军
林海
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Peking University Shenzhen Graduate School
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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
    • H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN heterojunction type
    • 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
    • H01L31/0248—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
    • H01L31/0256—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 characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • H—ELECTRICITY
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    • 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
    • H01L31/0248—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
    • H01L31/0256—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 characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
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    • 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
    • H01L31/0248—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
    • H01L31/0256—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 characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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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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Abstract

The application discloses a self-bias photoelectric detector and a preparation method and application thereof. The self-bias photoelectric detector comprises a substrate and a photoelectric structure fixed on the substrate, wherein the photoelectric structure comprises a photosensitive semiconductor layer, a blocking semiconductor layer and a counter electrode thin film layer; the photosensitive semiconductor layer is an n-type semiconductor material layer formed by cadmium sulfide; the barrier semiconductor layer is an n-type semiconductor material layer formed by titanium dioxide and/or metal-doped titanium dioxide. The application discloses self-bias photoelectric detector adopts the cadmium sulfide as photosensitive semiconductor layer, and titanium dioxide and/or metal doping titanium dioxide are as stopping semiconductor layer, and the CdS layer has good photosensitive characteristic, and the cooperation titanium dioxide forms the semiconductor junction, can reduce the leakage current, improves the photoelectric response effect. The self-bias photoelectric detector has the advantages of high reliability, low forward working voltage and high light extraction efficiency.

Description

Self-bias photoelectric detector and preparation method and application thereof
Technical Field
The application relates to the technical field of photoelectric detectors, in particular to a self-bias photoelectric detector and a preparation method and application thereof.
Background
The photodetector is a key device of future optical chip technology, optoelectronic integration technology, which requires the photodetector to have sufficiently high responsivity and response speed. The device transparentization and the ultraviolet entering of the response wave band can enable the light detector to work under sunlight, and also can enable the detector to be integrated under a screen, integrated on glass or prepared into full-transparent photoelectric detection. The self-powered detector has the characteristics of energy conservation, permanent work and convenience in integration, and is researched by people in a large quantity. Recently, the direct current and alternating current nanometer generator based on the self-powered photoelectric detector has attracted great interest. Self-biased detectors are highly sensitive, but self-biased photodetectors do not have photocurrent gain. Therefore, the responsivity of most of the existing self-powered optical detectors is not high, namely the photocurrent intensity under the same illumination intensity is not high.
Therefore, how to improve the responsivity of the self-biased photodetector remains the focus of research in the field.
Disclosure of Invention
The application aims to provide an improved self-bias photoelectric detector and a preparation method and application thereof.
The following technical scheme is adopted in the application:
one aspect of the present application discloses a self-biased photodetector, which includes a substrate and a photoelectric structure fixed on the substrate, the photoelectric structure including a photosensitive semiconductor layer and a barrier semiconductor layer, and a counter electrode thin film layer; the photosensitive semiconductor layer is an n-type semiconductor material layer formed by cadmium sulfide; the barrier semiconductor layer is an n-type semiconductor material layer formed by titanium dioxide and/or metal-doped titanium dioxide.
It is noted that the inventive design of the self-biased photodetector of n-n type semiconductor material layer of the present application employs TiO2Or metal doped TiO2Forming a semiconductor junction with CdSAnd quick response is realized. Compared with the prior art, the self-bias photoelectric detector has the advantages that 1) the CdS layer has good photosensitive property; 2) single CdS layer with large photoelectric leakage current and TiO application2Or metal doped TiO2The layer and CdS form a semiconductor junction, so that leakage current is reduced, and a photoelectric response effect is improved; 3) transparent electrodes such as ITO, FTO, AZO and the like are adopted, and transparent photoelectric detectors with different requirements can be manufactured. For example, a zinc oxide based transparent conductive electrode CdS/TiO2The base photoelectric detection chip has high reliability, low forward working voltage and high light extraction efficiency, and provides an effective method and a way for realizing the high-efficiency and low-cost photoelectric detection chip. It is to be understood that, in the self-bias photodetector of the present application, the order of the photosensitive semiconductor layer and the barrier semiconductor layer may be switched, for example, the structural order of the substrate + photosensitive semiconductor layer + barrier semiconductor layer may be adopted, and the structural order of the substrate + barrier semiconductor layer + photosensitive semiconductor layer may also be adopted.
In one implementation of the present application, the doping element of the metal-doped titanium dioxide is niobium and/or tantalum.
Preferably, the doping amount of niobium is 0.1 to 20% of the total weight of the barrier semiconductor layer, and the doping amount of tantalum is 0.1 to 20% of the total weight of the barrier semiconductor layer.
Preferably, the doping amount of niobium is 1.5-7% of the total weight of the barrier semiconductor layer, and the doping amount of tantalum is 1.5-7% of the total weight of the barrier semiconductor layer.
In one implementation of the present application, the barrier semiconductor layer has a thickness of 5-500 nm.
In one implementation of the present application, the thickness of the photosensitive semiconductor layer is 5-500 nm.
In one implementation of the present application, the substrate is glass, conductive glass, a flexible substrate, a quartz plate, or sapphire.
In one implementation of the present application, the counter electrode thin film layer is a conductive thin film formed by at least one of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, nano silver wires, and carbon paste.
The application also discloses an application of the self-bias photoelectric detector in the photoelectric detection chip.
The application further discloses a photoelectric detection chip adopting the self-bias photoelectric detector.
The application also discloses a preparation method of the self-bias photoelectric detector, which comprises the steps of carrying out magnetron sputtering deposition on a photosensitive semiconductor layer and a barrier semiconductor layer on a substrate, carrying out annealing treatment after deposition is finished, and then preparing a counter electrode thin film layer, namely obtaining the self-bias photoelectric detector.
In one implementation of the present application, the pressure of magnetron sputtering is 0.2 to 5Pa, and the power is 5 to 200W.
Preferably, the annealing treatment is carried out under the condition of keeping the temperature at 200-450 ℃ for 10-60 minutes in air, vacuum or inert environment.
The beneficial effect of this application lies in:
the application discloses self-bias photoelectric detector adopts the cadmium sulfide as photosensitive semiconductor layer, and titanium dioxide and/or metal doping titanium dioxide are as stopping semiconductor layer, and the CdS layer has good photosensitive characteristic, and the cooperation titanium dioxide forms the semiconductor junction, can reduce the leakage current, improves the photoelectric response effect. The self-bias photoelectric detector has the advantages of high reliability, low forward working voltage and high light extraction efficiency.
Drawings
FIG. 1 is a TEM observation result of a section of a self-bias photoelectric detector in the embodiment of the present application;
FIG. 2 is a response curve of a self-biased photodetector illuminated at 440nm and 550nm in an embodiment of the present application;
FIG. 3 is an AFM image of an NTO film in an example of the present application;
FIG. 4 is an SEM surface topography of a CdS thin film in the example of the present application.
Detailed Description
The research of the application finds that the main reason of slow response of the conventional self-bias photoelectric detector is that the main current mechanism of the conventional pn-junction self-supply photoelectric detector is that electrons and holes move from two ends to the middle of the device respectively, and recombination current is caused in the middle of the device. Such current flow causes no matter whetherBoth the on-time and the fall-time become relatively slow. The self-powered photoelectric detector of the nn-type heterojunction is creatively prepared by tuning the heterojunction interface energy band, and at the moment, the current mechanism of the device is mainly drift current of electrons instead of composite current of electron-hole pairs, so that the turn-on time and the turn-off time are greatly shortened. CdS/TiO of the present application2The self-bias photoelectric detection-based chip has excellent performance in visible light wave band wave bands and has wide application prospect in the aspects of photoelectric detection, image recognition and the like. CdS/TiO in the present application2In the photodetector, TiO2And the FTO conductive film is used as a window layer of the detector, and the CdS is used as a light absorption layer, so that the device is sensitive to visible light and near ultraviolet parts below 550 nm. The reason for selecting the two materials is that an nn type heterojunction can be formed through adjustment of an energy band and an interface, at the moment, drift current is dominant, the internal resistance of the device is low, and the photoelectric response of the device under a high-speed condition can be greatly improved. CdS/TiO of the present application2The base photoelectric detection chip is an effective way for realizing the high-efficiency photoelectric chip.
The present application will be described in further detail with reference to specific examples. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application.
Examples
In the self-bias photodetector of the present example, the substrate is FTO conductive glass, the niobium-doped titanium oxide thin film and the CdS film are respectively prepared on the FTO conductive glass by sputtering, and finally, silver paste is printed as an electrode to prepare the self-bias photodetector of the present example. The preparation method comprises the following steps:
1. and sequentially soaking the FTO conductive glass by using acetone, alcohol and deionized water, and then carrying out ultrasonic cleaning on the soaked FTO conductive glass.
2. Preparing a niobium-doped titanium oxide film on FTO conductive glass by adopting a vacuum sputtering method, wherein the pressure of a sputtering cavity is 0.3Pa, the atmosphere of the sputtering cavity is argon, the substrate temperature is 25 ℃, the sputtering power is 5W, the deposition rate is 10nm/min, the sputtering time is 30 minutes, and the niobium-doped titanium dioxide film with the thickness of 300nm is prepared, wherein the doping amount of niobium is 1 percent of the total weight of the barrier semiconductor layer. After the sputtering is finished, the sample is placed in an inert atmosphere to be heated to 420 ℃, the temperature is kept for 30 minutes, and the sample is cooled to room temperature to obtain the niobium-doped titanium oxide film with the preferred crystal orientation, namely the barrier semiconductor layer of the embodiment.
3. Vacuum sputtering CdS film with the thickness of 480nm, the sputtering power is 8W, and the sputtering time is 16 minutes at the deposition rate of 30 nm/min. And after the sputtering is finished, placing the sample in an inert atmosphere, heating to 400 ℃, preserving the heat for 20 minutes, and cooling to room temperature to obtain the highly-crystallized CdS film. The annealing process is favorable for reducing dangling bonds and in-vivo defects generated by sputtering and simultaneously reducing NTO/CdS or TiO2The interface state of/CdS strengthens lattice matching.
4. Printing a layer of silver paste on the surface by adopting a non-vacuum printing method to serve as an electrode, and drying the silver paste in air at 80 ℃ to finally obtain the FTO/TiO2A self-bias photoelectric detector with a Nb/CdS/Ag structure.
The self-biased photodetector prepared in this example was subjected to TEM cross-sectional observation, and the result is shown in fig. 1. As is evident from FIG. 1, the preparation of this example yields FTO/TiO2A Nb/CdS structural layer.
The self-biased photodetector prepared in this example was tested for operating voltage and light extraction efficiency, and the results are shown in fig. 2, where fig. 2 shows the response curves of the self-biased photodetector of this example at 440nm and 550nm illumination. The results show that the self-biased photodetector of this example has a low forward operating voltage and high light extraction efficiency.
In this example, 20 self-bias photodetectors were repeatedly prepared and tested according to the above method, and the results were consistent, with a deviation of less than 5%, which shows that the self-bias photodetectors of this example have high reliability and stability.
Based on the above tests, the sputtering power of step 2 and step 3 was further tested in this example, and the AFM image of the NTO thin film of step 2 is shown in fig. 3. In fig. 3, (a) is a barrier semiconductor layer prepared at a power of 60W, (b) is a barrier semiconductor layer prepared at a power of 120W, and (c) is a barrier semiconductor layer prepared at a power of 180W. The results show that the NTO film has the best flatness under the condition of 120W.
And (3) sputtering the CdS film at the power of 15W, 25W, 30W and 35W respectively, wherein the SEM surface topography is shown in FIG. 4. In fig. 4, (a) is a diagram of a 15W sputtered CdS film, (b) is a diagram of a 25W sputtered CdS film, (c) is a diagram of a 30W sputtered CdS film, and (d) is a diagram of a 35W sputtered CdS film. The results show that the grain size is the largest and the compactness is the best under the condition of 30W, and the flatness is the best under the condition of 35W.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended that the present application be limited to the specific embodiments thereof. It will be apparent to those skilled in the art from this disclosure that many more simple derivations or substitutions can be made without departing from the spirit of the disclosure.

Claims (10)

1. A self-biasing photodetector, characterized by: the photoelectric structure comprises a substrate and a photoelectric structure fixed on the substrate, wherein the photoelectric structure comprises a photosensitive semiconductor layer, a blocking semiconductor layer and a counter electrode thin film layer;
the photosensitive semiconductor layer is an n-type semiconductor material layer formed by cadmium sulfide;
the barrier semiconductor layer is an n-type semiconductor material layer formed by titanium dioxide and/or metal-doped titanium dioxide.
2. The self-biasing photodetector of claim 1, wherein: the doping element of the metal-doped titanium dioxide is niobium and/or tantalum;
preferably, the doping amount of niobium is 0.1-20% of the total weight of the barrier semiconductor layer, and the doping amount of tantalum is 0.1-20% of the total weight of the barrier semiconductor layer;
preferably, the doping amount of niobium is 1.5-7% of the total weight of the barrier semiconductor layer, and the doping amount of tantalum is 1.5-7% of the total weight of the barrier semiconductor layer.
3. The self-biasing photodetector of claim 1, wherein: the thickness of the barrier semiconductor layer is 5-500 nm.
4. The self-biasing photodetector of claim 1, wherein: the thickness of the photosensitive semiconductor layer is 5-500 nm.
5. The self-biased photodetector of any one of claims 1 to 4, wherein: the substrate is glass, conductive glass, a flexible substrate, a quartz plate or sapphire.
6. The self-biased photodetector of any one of claims 1 to 4, wherein: the counter electrode film layer is a conductive film formed by at least one of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, nano silver wires and carbon paste.
7. Use of a self-biasing photodetector according to any of claims 1-6 in a photodetection chip.
8. A photodetection chip employing the self-bias photodetector as claimed in any one of claims 1 to 6.
9. The method for producing a self-bias photodetector as claimed in any one of claims 1 to 6, wherein: the method comprises the steps of depositing a photosensitive semiconductor layer and a barrier semiconductor layer on a substrate through magnetron sputtering, carrying out annealing treatment after deposition is finished, and then preparing a counter electrode thin film layer to obtain the self-bias photoelectric detector.
10. The method of claim 9, wherein: the pressure of the magnetron sputtering is 0.2-5 Pa, and the power is 5-200W;
preferably, the annealing treatment is carried out under the condition of keeping the temperature at 200-450 ℃ for 10-60 minutes in air, vacuum or inert environment.
CN202210256024.8A 2022-03-15 2022-03-15 Self-bias photoelectric detector and preparation method and application thereof Pending CN114695580A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102245538A (en) * 2008-12-12 2011-11-16 康宁股份有限公司 Titania-half metal composites as high-temperature thermoelectric materials
CN103163115A (en) * 2011-12-11 2013-06-19 欧普图斯(苏州)光学纳米科技有限公司 Multi-layer variable microstructure capable of sensing substance
CN104701017A (en) * 2014-12-26 2015-06-10 北京大学深圳研究生院 Titanium dioxide film photo-electrode and preparation method and application thereof
WO2018028244A1 (en) * 2015-09-18 2018-02-15 北京大学深圳研究生院 Transparent conductive film, preparation method therefor and application thereof
CN107705873A (en) * 2017-07-31 2018-02-16 北京大学深圳研究生院 A kind of transparent conducting glass and its preparation method and application
CN111139449A (en) * 2019-12-31 2020-05-12 深圳信息职业技术学院 Zinc oxide based transparent electrode photoelectric detector and preparation method thereof
CN111952384A (en) * 2020-07-02 2020-11-17 深圳大学 Photoelectric detector and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102245538A (en) * 2008-12-12 2011-11-16 康宁股份有限公司 Titania-half metal composites as high-temperature thermoelectric materials
CN103163115A (en) * 2011-12-11 2013-06-19 欧普图斯(苏州)光学纳米科技有限公司 Multi-layer variable microstructure capable of sensing substance
CN104701017A (en) * 2014-12-26 2015-06-10 北京大学深圳研究生院 Titanium dioxide film photo-electrode and preparation method and application thereof
WO2018028244A1 (en) * 2015-09-18 2018-02-15 北京大学深圳研究生院 Transparent conductive film, preparation method therefor and application thereof
CN107705873A (en) * 2017-07-31 2018-02-16 北京大学深圳研究生院 A kind of transparent conducting glass and its preparation method and application
CN111139449A (en) * 2019-12-31 2020-05-12 深圳信息职业技术学院 Zinc oxide based transparent electrode photoelectric detector and preparation method thereof
CN111952384A (en) * 2020-07-02 2020-11-17 深圳大学 Photoelectric detector and preparation method thereof

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