CN111952387A - Ultraviolet, visible and infrared wide-spectrum photoelectric detector and preparation method thereof - Google Patents
Ultraviolet, visible and infrared wide-spectrum photoelectric detector and preparation method thereof Download PDFInfo
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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
- H01L31/0248—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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
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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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035218—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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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
- H01L31/10—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 at least one potential-jump barrier or surface barrier, 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 or surface barrier
- H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the PN heterojunction type
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Abstract
The invention discloses an ultraviolet, visible and infrared wide-spectrum photoelectric detector and a preparation method thereof, wherein the preparation method comprises the following steps: selecting a cleaned glass substrate; preparing an electrode array on the glass substrate, wherein the electrode array comprises a plurality of metal electrodes which are arranged at intervals; spraying nano fibers on the glass substrate with the electrode array to prepare a ZnO nanowire film covering the electrode array; spin-coating Ge quantum dots on the ZnO nanowire film to prepare a Ge quantum dot film; and preparing a metal film on the back of the glass substrate. The photoelectric detector prepared by the invention has a ZnO nanowire and Ge quantum dot composite structure, the advantages of the two materials can be combined, and the invention realizes wide-spectrum detection by adopting a low-cost method.
Description
Technical Field
The invention belongs to the technical field of detectors, and particularly relates to an ultraviolet, visible and infrared wide-spectrum photoelectric detector and a preparation method thereof.
Background
At present, most photoelectric detectors are photoelectric detection diodes based on PN junctions, and the photoelectric detectors with wide spectral response are widely applied to the fields of image sensing, chemical/biological sensing, communication and the like. The detection of ultraviolet light and infrared light has a large market for military and civil use, for example, flight targets of a large amount of ultraviolet radiation released in tail smoke of a solar blind area can be detected in real time in an ultraviolet band, and the detection of the ultraviolet light and the infrared light can be used for resource investigation, environment monitoring, medical diagnosis, night vision imaging and the like in an infrared region.
At present, the wide-spectrum photoelectric detector on the market has high preparation cost and complex preparation process, and a great amount of time and energy are required to be invested to explore a preparation method. Therefore, it is an urgent need to provide a simple and mature method with low manufacturing cost to prepare a wide-spectrum photodetector.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an ultraviolet, visible and infrared wide-spectrum photoelectric detector and a preparation method thereof. The technical problem to be solved by the invention is realized by the following technical scheme:
a method for preparing an ultraviolet, visible and infrared wide-spectrum photoelectric detector comprises the following steps:
selecting a cleaned glass substrate;
preparing an electrode array on the glass substrate, wherein the electrode array comprises a plurality of metal electrodes which are arranged at intervals;
spraying nano fibers on the glass substrate with the electrode array to prepare a ZnO nanowire film covering the electrode array;
spin-coating Ge quantum dots on the ZnO nanowire film to prepare a Ge quantum dot film;
and preparing a metal film on the back of the glass substrate.
In one embodiment of the present invention, selecting a cleaned glass substrate comprises:
selecting the glass substrate;
and sequentially carrying out ultrasonic treatment on the glass substrate by using deionized water, ethanol and toluene to obtain the cleaned glass substrate.
In one embodiment of the present invention, preparing an electrode array on the glass substrate comprises:
and evaporating the electrode array on the glass substrate by using an evaporation process.
In one embodiment of the present invention, spraying nanofibers on the glass substrate on which the electrode array is prepared to prepare a ZnO nanowire film covering the electrode array, includes:
preparing a precursor solution;
absorbing the precursor solution, and spraying the nano-fibers on the glass substrate with the electrode array by adopting an electrostatic spinning process;
and annealing the nano-fibers to prepare the ZnO nanowire film covering the electrode array, wherein the annealing temperature is 600 ℃, and the annealing time is 4 hours.
In one embodiment of the invention, preparing a precursor solution comprises:
dissolving zinc nitrate in a DMF solution to obtain a first mixed solution;
and adding polyvinylpyrrolidone into the first mixed solution, and stirring to obtain a precursor solution.
In one embodiment of the present invention, the spin coating of Ge quantum dots on the ZnO nanowire film to prepare a Ge quantum dot film comprises:
preparing Ge quantum dots;
preparing a second mixed solution by using tetraethoxysilane and ethanol;
preparing a third mixed solution by using ammonia water, distilled water and ethanol;
adding the third mixed solution into the second mixed solution, and stirring to prepare a fourth mixed solution;
dissolving the Ge quantum dots in the fourth mixed solution and carrying out ultrasonic treatment to prepare a fifth mixed solution, wherein the concentration of the solution of the Ge quantum dots dissolved in the fourth mixed solution is 20mg/ml, and the time of ultrasonic treatment is 24 h;
and spin-coating the fifth mixed solution on the ZnO nanowire film to prepare the Ge quantum dot film.
In one embodiment of the present invention, the preparation of Ge quantum dots comprises:
adding GeO2And PVP were dissolved in the NaOH solution, and stirred to prepare a sixth mixed solution;
adding an HCl solution to the sixth mixed solution to make the pH value of the sixth mixed solution between 5 and 1 l;
heating the sixth mixed solution, and then adding NaBH to the sixth mixed solution4Heating the ice water solution to prepare a seventh mixed solution;
and sequentially carrying out centrifugal treatment on the seventh mixed solution by using deionized water and ethanol, and then sequentially carrying out drying treatment and vacuum annealing treatment to prepare the Ge quantum dots.
In one embodiment of the present invention, preparing a metal thin film on the back surface of the glass substrate includes:
and preparing the metal film on the back of the glass substrate by adopting an electron beam evaporation process, wherein the metal film is made of Au.
An embodiment of the present invention further provides an ultraviolet, visible, and infrared wide-spectrum photodetector, which is manufactured by using the method for manufacturing an ultraviolet, visible, and infrared wide-spectrum photodetector described in any one of the embodiments, and the ultraviolet, visible, and infrared wide-spectrum photodetector includes:
a metal thin film;
a glass substrate located over the metal thin film;
the electrode array is positioned on the glass substrate and comprises a plurality of metal electrodes which are arranged at intervals;
the ZnO nanowire film is positioned on the electrode array and the glass substrate, and the ZnO nanowire film covers the electrode array;
and the Ge quantum dot film is positioned on the ZnO nanowire film.
In one embodiment of the present invention, the metal thin film is made of Au, and the metal electrode is made of Au.
The invention has the beneficial effects that:
the invention provides a preparation method of a wide-spectrum photoelectric detector for ultraviolet, visible and infrared rays, because the forbidden bandwidth of zinc oxide is 3.4eV, which has high photosensitivity to ultraviolet light, by preparing zinc oxide in a one-dimensional Nanowire (NWs) form, while the one-dimensional nano-wire has unique geometrical and electronic characteristics, can provide a large width-to-length ratio, has great effect on improving the light absorption response, and the forbidden band width of germanium is 0.67eV, has stronger light response in visible light and infrared wave bands, the zero-dimensional quantum dots have larger quantum confinement effect, the invention is widely applied to infrared light-emitting diodes and infrared photoelectric detectors, so that the photoelectric detector prepared by the invention has a structure of compounding ZnO nanowires and Ge quantum dots, the advantages of the two materials can be combined, and the invention realizes the detection of a wide spectrum by adopting a low-cost method.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic diagram of a nanowire structure provided in the prior art;
FIG. 2 is a schematic flow chart of a fabrication process of a photodetector provided in the prior art;
FIG. 3 is a schematic flow chart of a method for fabricating a wide ultraviolet, visible and infrared spectrum photodetector according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of an ultraviolet, visible, and infrared wide-spectrum photodetector according to an embodiment of the present invention.
Description of reference numerals:
a glass substrate-10; electrode array-20; ZnO nanowire film-30; ge quantum dot film-40; a metal film-50.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example one
The Ge heterojunction nanowire structure proposed in the article "Broadband 400-2400nm Ge heterojunction nanowire detector structured by three-dimensional Ge coherence detection technique" published in 2019 by Linguanning et al can realize detection in the range of 400-2400 nm. The preparation process comprises the following steps: firstly, growing 5nm Si and 99nm Si on an insulator Silicon (SOI) substrate0.76Ge0.24Layer, 95nm Si is formed in the buried oxide layer at 1150 deg.C0.67Ge0.3And (3) a layer. Then using Buffered Oxide Etchant (BOE) to remove surface SiO generated in the planar Ge agglomeration process2To define a pattern on the SiGe layer. The upper edge of the buried oxide layer is [110 ] formed by Electron Beam Lithography (EBL) and Reactive Ion Etching (RIE)]The insulator nanowires are prepared by orientation, and the pattern of the insulator nanowires is shown in fig. 1, wherein fig. 1 is a schematic structural diagram of a nanowire provided by the prior art. NW with a total length of 45 μm was fixed at a size of 50X 50 μm2The two spacers of (2) have different widths in the longitudinal direction, and the NW may be divided into three parts, i.e., a first part, a second part and a third part at both ends of the first part, wherein the second part and the third part have a length of 20 μm and a width of 677nm, and the first part has a length of 5 μm and a width of 200 nm. Finally, the patterned sample was loaded into an oven,the three-dimensional Ge condensation process was performed at 900 ℃. The entire condensation process included 10 minutes of oxidation followed by 10 minutes of annealing. The oxidation process is carried out under the condition that the oxygen concentration is 99.5%, and the annealing process is carried out under the condition that the purity is 99.999% respectively. However, this method is expensive and complicated.
Zhengzhi et al published in 2016 as "An Enhanced UV-Vis-NIR An d Flexible phosphor Based on Electrospun ZnO Nanowire Array/PbS Quantum Dots Film heterogeneous chromatography". The article provides a ZnO nanowire matrix/PbS quantum dot combined structure, and can realize wide-spectrum photoelectric detection from ultraviolet-visible-near infrared (930 nm). Referring to fig. 2, fig. 2 is a schematic flow chart of a manufacturing process of a photodetector provided in the prior art, and a manufacturing method thereof is shown as follows: preparing a mixed solution of zinc nitrate and polyethylene Terra and spraying the mixed solution on a cleaned glass sheet by adopting an electrostatic spinning process, and then annealing at 500 ℃ for 3 hours. And spin-coating the prepared PbS solution on a glass sheet at the speed of 4000r/min, dripping a few drops of acetonitrile solution, standing for 5min, and manufacturing Au electrodes at two ends of the device by adopting an evaporation method. However, PbS is toxic, limiting its use in many applications. Moreover, the forbidden band width of PbS is 1.3ev, the cut-off wavelength of infrared is 930nm, and it cannot be applied to the communication band.
Therefore, referring to fig. 3 and fig. 4, fig. 3 is a schematic flow chart of a method for manufacturing an ultraviolet, visible and infrared wide-spectrum photodetector according to an embodiment of the present invention, and fig. 4 is a schematic structural view of an ultraviolet, visible and infrared wide-spectrum photodetector according to an embodiment of the present invention. The embodiment provides a method for manufacturing an ultraviolet, visible and infrared wide-spectrum photoelectric detector, which comprises the following steps:
and step 1, selecting the cleaned glass substrate 10.
Step 1.1, selecting a glass substrate 10.
For example, the glass substrate 10 has a size of 1cm × 1 cm.
And step 1.2, sequentially carrying out ultrasonic treatment on the glass substrate 10 by using deionized water, ethanol and toluene to obtain the cleaned glass substrate 10.
Specifically, the glass substrate 10 is first subjected to ultrasonic treatment with deionized water, for example, for 15min, then the glass substrate 10 is subjected to ultrasonic treatment with ethanol, for example, for 15min, and finally the glass substrate 10 is subjected to ultrasonic treatment with toluene, for example, for 15min, thereby completing the cleaning of the glass substrate 10.
And 2, preparing an electrode array 20 on the glass substrate 10, wherein the electrode array 20 comprises a plurality of metal electrodes which are arranged at intervals.
Specifically, an electrode array is vapor-deposited on the glass substrate 10 by an evaporation process, wherein the metal electrode is cylindrical and has a radius of, for example, 1mm, the gap between the two metal electrodes is, for example, 1mm, and the material of the metal electrode is, for example, Au.
And 3, spraying the nano fibers on the glass substrate 10 with the electrode array 20 to prepare the ZnO nanowire film 30 covering the electrode array 20.
And 3.1, preparing a precursor solution.
And 3.11, dissolving zinc nitrate in the DMF solution to obtain a first mixed solution.
Specifically, zinc nitrate (Zn (NO)3)2·6H2O) is dissolved in a DMF (N, N-dimethylformamide) solution, and a mixed solution of zinc nitrate and the DMF solution is a first mixed solution.
For example, 2g of zinc nitrate (Zn (NO)3)2·6H2O) in 12ml of DMF (N, N-dimethylformamide).
And 3.12, adding polyvinylpyrrolidone into the first mixed solution, and stirring to obtain a precursor solution.
Specifically, polyvinylpyrrolidone (PVP) was added to the first mixed solution, and a uniform precursor solution was formed by continuous stirring, the amount of polyvinylpyrrolidone being 6g, for example.
And 3.2, absorbing the precursor solution, and spraying the nano fibers on the glass substrate 10 with the electrode array 20 by adopting an electrostatic spinning process.
Specifically, the precursor solution is sucked, and the nanofibers are sprayed on the glass substrate 10 on which the electrode array 20 is evaporated by using an electrospinning process (the distance from the needle to the collector is 14cm, the voltage is set to 18kv, and the spinning time is 25min), for example, 1ml of the precursor solution is sucked.
And 3.3, annealing the nano fibers to prepare the ZnO nanowire film 30 covering the electrode array 20, wherein the annealing temperature is 600 ℃, and the annealing time is 4 hours.
Specifically, the prepared nano-fiber is subjected to heat treatment for 4 hours in the air at the temperature of 600 ℃, and the heating rate is 6 ℃ min-1The nanofiber after heat treatment is the ZnO nanowire film 30, and the annealing temperature of 600 ℃ and the annealing time of 4h are the optimal conditions selected through a large number of experiments.
And 4, spin-coating the Ge quantum dots on the ZnO nanowire film 30 to prepare the Ge quantum dot film 40.
And 4.1, preparing the Ge quantum dots.
Step 4.11, GeO2And PVP (polyvinylpyrrolidone) were dissolved in the NaOH solution, and stirring was performed to prepare a sixth mixed solution.
Specifically, GeO2And PVP is dissolved in a flask containing NaOH solution, and the mixture is stirred under a magnetic stirrer to obtain a transparent and clear solution, namely a sixth mixed solution.
For example, 0.26g of GeO is weighed2And 0.01g of PVP was dissolved in a flask containing 10mL of 0.15M NaOH solution and stirred with a magnetic stirrer to give a clear, clear solution.
And 4.12, adding an HCl solution into the sixth mixed solution to ensure that the pH value of the sixth mixed solution is between 5 and 1 l.
Specifically, 0.5M HCl solution is added to the sixth mixed solution to adjust the pH of the sixth mixed solution to between 5 and 1 l.
Step 4.13, heating the sixth mixed solution, and then adding NaBH into the sixth mixed solution4The ice-water solution was subjected to heating to prepare a seventh mixed solution.
Specifically, a sixth mixed solution with the pH value of 5-1l is placed in a water bath for preheating, and then NaBH is added into the preheated sixth mixed solution4Ice water solution, adding NaBH4And heating the mixed solution of the ice water solution and the sixth mixed solution in a water bath kettle for reaction, and finally obtaining a dark brown solution, wherein the dark brown solution is the seventh mixed solution.
For example, the sixth mixed solution with a pH of 5-1l is preheated in a 60 ℃ water bath for 5 minutes, after which 10mL of 0.32M NaBH is added4And (3) carrying out ice water solution, and reacting the mixed solution in a water bath kettle at the temperature of 60 ℃ for 3 hours to obtain a dark brown solution.
And 4.14, sequentially utilizing deionized water and ethanol to carry out centrifugal treatment on the seventh mixed solution, and then sequentially carrying out drying treatment and vacuum annealing treatment to prepare the Ge quantum dots.
Specifically, the seventh mixed solution is first centrifuged for a plurality of times with deionized water, for example, the number of times of centrifugation is 3, then centrifuged for a plurality of times with ethanol, for example, the number of times of centrifugation is 3, and then placed in a vacuum drying oven to be dried for a period of time at room temperature, for example, 6 hours, to obtain a brown powder sample, which is a Ge nanocrystal, and then a portion of the synthesized Ge nanocrystal is uniformly spread in a quartz boat and subjected to vacuum annealing in a vacuum annealing furnace, wherein the vacuum annealing process includes: firstly, heating a tube furnace to 600 ℃ at the speed of 6 ℃/min, carrying out constant-temperature heat preservation treatment for one hour, and finally taking out a sample after the furnace temperature is naturally cooled, wherein the sample is the Ge quantum dot.
And 4.2, preparing a second mixed solution by using tetraethoxysilane and ethanol.
Specifically, the tetraethoxysilane and the ethanol are placed in a beaker and are uniformly stirred at room temperature to obtain a mixed solution of the tetraethoxysilane and the ethanol, and the mixed solution is a second mixed solution.
For example, 0.1mol of ethyl orthosilicate and 3.6mol of ethanol are placed in a beaker and stirred at room temperature.
And 4.3, preparing a third mixed solution by using ammonia water, distilled water and ethanol.
Specifically, ammonia water, distilled water and ethanol are taken and placed into another beaker, and the mixture is stirred uniformly at room temperature to obtain a mixed solution of the ammonia water, the distilled water and the ethanol, wherein the mixed solution is a third mixed solution.
For example, 0.07mol of ammonia water, 0.2mol of distilled water and 0.1mol of ethanol are taken and put into another beaker to be stirred for 30min until the mixture is stirred uniformly.
And 4.4, adding the third mixed solution into the second mixed solution, and stirring to prepare a fourth mixed solution.
Specifically, slowly dripping the third mixed solution into the second mixed solution, uniformly mixing, putting into a 30 ℃ water bath tank, stirring and reacting for 4 hours, taking out, cooling to room temperature, sealing and storing, wherein the stored mixed solution is a silicon dioxide solution, and the silicon dioxide solution is a fourth mixed solution.
And 4.5, dissolving the Ge quantum dots in the fourth mixed solution and carrying out ultrasonic treatment to prepare a fifth mixed solution, wherein the concentration of the solution of the Ge quantum dots dissolved in the fourth mixed solution is 20mg/ml, and the ultrasonic treatment time is 24 h.
Specifically, Ge quantum dots are dissolved in a silicon dioxide solution to prepare a solution with the concentration of 20mg/ml, the solution is subjected to ultrasonic treatment for 24 hours, the Ge quantum dots can be dispersed more uniformly, and the solution after the ultrasonic treatment is a fifth mixed solution, wherein the concentration of 20mg/ml can ensure that the Ge quantum dots are uniformly dispersed and can also ensure that the Ge quantum dots are spin-coated on a device to have obvious optical response.
And 4.6, spin-coating the fifth mixed solution on the ZnO nanowire film 30 to prepare the Ge quantum dot film 40.
Specifically, the fifth mixed solution is sucked and spin-coated on the ZnO nanowire film 30, and the spin-coating is performed for multiple times until a layer of film is formed, which is the Ge quantum dot film 40.
And 5, preparing a metal film 50 on the back of the glass substrate 10.
Specifically, the metal thin film 50 is prepared on the back surface of the glass substrate 10 by using an electron beam evaporation process, the material of the metal thin film 50 is Au, thereby enabling to enhance the absorption of light by the absorption layer, and the thickness of the metal thin film 50 is, for example, 200 nm.
The composite structure of the ZnO nanowire and the Ge quantum dot prepared by the invention can realize detection of a wide-range waveband from ultraviolet-visible-infrared, and compared with the composite structure of the PbS quantum dot, the detection range can reach a communication waveband, because the forbidden bandwidth of zinc oxide is 3.4eV, the composite structure has high photosensitivity to ultraviolet light, and the one-dimensional ZnO nanowire prepared by the electrostatic spinning process has the characteristics of small size, large specific surface area, high carrier mobility, adjustable light absorption and the like due to the unique geometrical and electronic characteristics of the one-dimensional ZnO nanowire and the one-dimensional NWs, so that the composite structure of the ZnO nanowire and the Ge quantum dot has excellent photoelectric characteristics. In addition, the forbidden band width of germanium is 0.67eV, the germanium has strong photoresponse in visible light and infrared bands, and zero-dimensional quantum dots have large quantum confinement effect and are widely applied to infrared light-emitting diodes and infrared photodetectors. Therefore, the photoelectric detector prepared by the invention has a structure of compounding the ZnO nanowire and the Ge quantum dot, the advantages of the two materials can be combined, and the invention realizes the detection of a wide spectrum by adopting a low-cost method.
The photoelectric detector prepared by the invention has simple preparation process and low cost, and in addition, if the ZnO nanowire prepared by the epitaxial process needs high substrate cleanliness and high vacuum degree, the requirement on equipment is high, and the price is expensive.
Example two
Referring to fig. 4 again, the present embodiment further provides an ultraviolet, visible and infrared wide spectrum photodetector based on the above embodiment, where the ultraviolet, visible and infrared wide spectrum photodetector is prepared by the preparation method of the above embodiment, and the photodetector includes:
the metal film 50, the material of the metal film 50 is Au;
a glass substrate 10 on the metal thin film 50;
the electrode array 20 is positioned on the glass substrate 10, and the electrode array 20 includes a plurality of metal electrodes arranged at intervals, and the metal electrodes are made of, for example, Au;
the ZnO nanowire film 30 is positioned above the electrode array 20 and the glass substrate 10, and the ZnO nanowire film 30 covers the electrode array 20;
and the Ge quantum dot film 40 is positioned on the ZnO nanowire film 20.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic data point described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples described in this specification can be combined and combined by those skilled in the art.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A method for preparing a wide-spectrum ultraviolet, visible and infrared photodetector is characterized by comprising the following steps:
selecting a cleaned glass substrate;
preparing an electrode array on the glass substrate, wherein the electrode array comprises a plurality of metal electrodes which are arranged at intervals;
spraying nano fibers on the glass substrate with the electrode array to prepare a ZnO nanowire film covering the electrode array;
spin-coating Ge quantum dots on the ZnO nanowire film to prepare a Ge quantum dot film;
and preparing a metal film on the back of the glass substrate.
2. The method of claim 1, wherein selecting a cleaned glass substrate comprises:
selecting the glass substrate;
and sequentially carrying out ultrasonic treatment on the glass substrate by using deionized water, ethanol and toluene to obtain the cleaned glass substrate.
3. The method of fabricating a broad ultraviolet, visible and infrared spectrum photodetector of claim 1, wherein fabricating an electrode array on said glass substrate comprises:
and evaporating the electrode array on the glass substrate by using an evaporation process.
4. The method of claim 1, wherein spraying nanofibers onto the glass substrate on which the electrode array is formed to form a ZnO nanowire film covering the electrode array comprises:
preparing a precursor solution;
absorbing the precursor solution, and spraying the nano-fibers on the glass substrate with the electrode array by adopting an electrostatic spinning process;
and annealing the nano-fibers to prepare the ZnO nanowire film covering the electrode array, wherein the annealing temperature is 600 ℃, and the annealing time is 4 hours.
5. The method of claim 4, wherein preparing a precursor solution comprises:
dissolving zinc nitrate in a DMF solution to obtain a first mixed solution;
and adding polyvinylpyrrolidone into the first mixed solution, and stirring to obtain a precursor solution.
6. The method of claim 1, wherein the spin coating of Ge quantum dots on the ZnO nanowire film to produce a Ge quantum dot film comprises:
preparing Ge quantum dots;
preparing a second mixed solution by using tetraethoxysilane and ethanol;
preparing a third mixed solution by using ammonia water, distilled water and ethanol;
adding the third mixed solution into the second mixed solution, and stirring to prepare a fourth mixed solution;
dissolving the Ge quantum dots in the fourth mixed solution and carrying out ultrasonic treatment to prepare a fifth mixed solution, wherein the concentration of the solution of the Ge quantum dots dissolved in the fourth mixed solution is 20mg/ml, and the time of ultrasonic treatment is 24 h;
and spin-coating the fifth mixed solution on the ZnO nanowire film to prepare the Ge quantum dot film.
7. The method of claim 6, wherein the step of preparing Ge quantum dots comprises:
adding GeO2And PVP were dissolved in the NaOH solution, and stirred to prepare a sixth mixed solution;
adding an HCl solution to the sixth mixed solution to make the pH value of the sixth mixed solution between 5 and 1 l;
heating the sixth mixed solution, and then adding NaBH to the sixth mixed solution4Heating the ice water solution to prepare a seventh mixed solution;
and sequentially carrying out centrifugal treatment on the seventh mixed solution by using deionized water and ethanol, and then sequentially carrying out drying treatment and vacuum annealing treatment to prepare the Ge quantum dots.
8. The method of claim 1, wherein forming a metal film on the back side of the glass substrate comprises:
and preparing the metal film on the back of the glass substrate by adopting an electron beam evaporation process, wherein the metal film is made of Au.
9. An ultraviolet, visible and infrared wide spectrum photodetector manufactured by the method for manufacturing an ultraviolet, visible and infrared wide spectrum photodetector according to any one of claims 1 to 8, comprising:
a metal thin film;
a glass substrate located over the metal thin film;
the electrode array is positioned on the glass substrate and comprises a plurality of metal electrodes which are arranged at intervals;
the ZnO nanowire film is positioned on the electrode array and the glass substrate, and the ZnO nanowire film covers the electrode array;
and the Ge quantum dot film is positioned on the ZnO nanowire film.
10. The broad ultraviolet, visible, and infrared photodetector of claim 9, wherein the metal thin film is made of Au, and the metal electrode is made of Au.
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