CN114464694B - Photoelectric detector and preparation method thereof - Google Patents
Photoelectric detector and preparation method thereof Download PDFInfo
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- CN114464694B CN114464694B CN202210023552.9A CN202210023552A CN114464694B CN 114464694 B CN114464694 B CN 114464694B CN 202210023552 A CN202210023552 A CN 202210023552A CN 114464694 B CN114464694 B CN 114464694B
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- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 131
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Classifications
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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
- H01L31/0256—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
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
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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
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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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- General Physics & Mathematics (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
- Light Receiving Elements (AREA)
Abstract
The application discloses a photoelectric detector and a preparation method thereof, wherein the photoelectric detector comprises an insulating substrate; a first electrode and a second electrode disposed on the insulating substrate at a distance from each other; the tin-doped molybdenum oxide/silicon heterojunction structure is connected with the first electrode and the second electrode, and is a heterojunction formed by the tin-doped molybdenum oxide layer and the silicon layer. The photoelectric detector provided by the embodiment of the application has at least the following beneficial effects: the photoelectric detector provided by the scheme has the advantages that the hybridization energy level is introduced into the tin-doped molybdenum oxide, the high absorptivity of infrared light is realized, the doped molybdenum oxide further forms a two-dimensional material heterojunction with an ideal interface with silicon, a built-in electric field can be formed at the interface of the tin-doped molybdenum oxide/silicon heterojunction, and photo-generated electron hole pairs are effectively separated, so that the near-infrared photoelectric detector has ultra-fast response time.
Description
Technical Field
The application relates to the technical field of semiconductor photoelectric devices, in particular to a photoelectric detector and a preparation method thereof.
Background
Two-dimensional materials are a general term for a large class of materials, and compared with conventional photoelectric materials, two-dimensional materials have many excellent and peculiar properties, such as ultrathin atomic layer thickness, band gap structure adjustable with thickness, excellent and anisotropic photoelectric properties, and photoelectric devices based on the two-dimensional materials have been studied greatly. Among them, layered two-dimensional molybdenum oxide (α -molybdenum oxide) is an important place and application in optoelectronic devices as a wide bandgap semiconductor material. The intrinsic wide band gap structure limits the spectrum range of the infrared photoelectric detector to ultraviolet band, so that the detection of near infrared band light can not be realized, but the light absorption of the infrared wavelength region can be realized by doping impurity energy level, so that the infrared photoelectric detector prepared based on doped molybdenum oxide has attracted extensive research interest. The tin-doped two-dimensional molybdenum oxide is introduced into impurity energy levels, so that high light absorptivity in an infrared region can be realized, meanwhile, the conductivity of the infrared region is improved, and efficient detection of infrared light is realized.
Disclosure of Invention
The present application aims to solve at least one of the technical problems existing in the prior art. Therefore, the application provides a photoelectric detector with excellent response speed and a preparation method thereof.
In a first aspect of the present application, there is provided a photodetector comprising:
an insulating substrate;
A first electrode and a second electrode disposed on the insulating substrate at a distance from each other;
The tin-doped molybdenum oxide/silicon heterojunction structure is connected with the first electrode and the second electrode, and is a heterojunction formed by the tin-doped molybdenum oxide layer and the silicon layer.
The photoelectric detector provided by the embodiment of the application has at least the following beneficial effects:
The photoelectric detector provided by the scheme has the advantages that the hybridization energy level is introduced into the tin-doped molybdenum oxide, the high absorptivity of infrared light is realized, the doped molybdenum oxide further forms a two-dimensional material heterojunction with an ideal interface with silicon, a built-in electric field can be formed at the interface of the tin-doped molybdenum oxide/silicon heterojunction, and photo-generated electron hole pairs are effectively separated, so that the near-infrared photoelectric detector has ultra-fast response time.
In some embodiments of the present application, the insulating substrate includes a first electrode, a silicon layer, a tin-doped molybdenum oxide layer, and a second electrode that overlap in that order.
In some embodiments of the application, the silicon layer is a multilayer single crystal silicon.
In some embodiments of the application, the silicon layer has a thickness of 30 to 300nm.
In some embodiments of the application, the tin-doped molybdenum oxide layer is a multilayer single crystal tin-doped molybdenum oxide.
In some embodiments of the application, the number of tin-doped molybdenum oxide layers is 2 to 100.
In some embodiments of the application, the first electrode and the second electrode are metal electrodes.
In some embodiments of the application, the material of the metal electrode is at least one of gold, silver, and aluminum.
In some embodiments of the application, the first electrode and the second electrode have a thickness of 50 to 150nm.
In a second aspect of the present application, a method for manufacturing a photodetector is provided, in which a tin-doped molybdenum oxide layer is manufactured by a thermal evaporation technology.
In the prior art, a solution method is mostly adopted for preparing tin doped molybdenum oxide, but in the experimental process, when the solution method is adopted for tin doping, the tin doping in the doped molybdenum oxide material is uneven, and the uneven doping leads to smaller conductivity, so that current is reduced, and finally the detection effect of the photoelectric detector is influenced. In contrast, the method of thermal evaporation plating is adopted in the scheme, so that doping is more uniform, the conductivity of the finally obtained tin-doped molybdenum oxide is larger, current is larger, and the detection effect of the photoelectric detector is better.
In some embodiments of the application, the steps of thermal evaporation are: the powder of molybdenum oxide and stannous salt is uniformly mixed and then evaporated onto an evaporation substrate by adopting a method of slow evaporation and then fast evaporation, wherein the evaporation speed of the slow evaporation is 0.1-0.5 nm/s, and the evaporation speed of the fast evaporation is 0.5-2 nm/s. The tin-doped molybdenum oxide obtained by vapor deposition has higher absorptivity in the infrared band by adopting a mode of combining slow vapor deposition and fast vapor deposition.
In some embodiments of the application, the slow evaporation time is 60 to 200 seconds.
In some embodiments of the application, the thickness of the tin-doped molybdenum oxide layer obtained after the rapid evaporation is completed is 200-500 nm.
In some embodiments of the present application, the vapor deposited substrate is an insulating substrate including, but not limited to, alumina, silica (e.g., quartz glass), sapphire, polyethylene terephthalate (PET), etc., or a conductive substrate including, but not limited to, fluorine doped tin oxide (FTO) glass, indium Tin Oxide (ITO) glass, etc.
In some embodiments of the present application, the method of manufacturing the photodetector comprises the steps of:
Preparing a tin-doped molybdenum oxide layer by a thermal evaporation technology;
Transferring the tin-doped molybdenum oxide layer onto a silicon layer of an insulating substrate to form a tin-doped molybdenum oxide/silicon heterojunction structure;
and a first electrode and a second electrode are arranged on the surface of the tin-doped molybdenum oxide/silicon heterojunction structure.
In some embodiments of the application, the silicon layer on the insulating substrate is obtained by reactive ion etching.
In some embodiments of the application, the thickness of the silicon layer on the insulating substrate is 30 to 300nm.
In some embodiments of the present application, the reactive ion etching is performed using a gas comprising at least one of trifluoromethane (CHF 3) and sulfur hexafluoride (SF 6). In the experimental process, it is found that the reactive ion etching can be effectively completed by adopting the trifluoromethane and the sulfur hexafluoride.
In some embodiments of the application, the etching power of the reactive ion etching is 100-350W.
In some embodiments of the application, the reactive ion etching gas flow is 15-25 scm.
In some embodiments of the application, the etching time of the reactive ion etching is 30 to 90 seconds.
In some embodiments of the application, the transfer temperature of the tin-doped molybdenum oxide layer to the silicon layer is below 25 ℃.
In some embodiments of the present application, the method further comprises the step of stripping the tin-doped molybdenum oxide layer from the evaporation substrate prior to transferring the tin-doped molybdenum oxide layer to the silicon layer.
In some embodiments of the application, the stripping is performed using polydimethylsiloxane when stripping the tin-doped molybdenum oxide layer from the evaporation substrate.
In some embodiments of the application, the number of stripped tin-doped molybdenum oxide layers is 2 to 100.
In some embodiments of the present application, the method for disposing the first electrode and the second electrode on the surface of the tin-doped molybdenum oxide/silicon heterojunction structure comprises: a metal material is vapor deposited on an insulating substrate to form a first electrode and a second electrode.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
Fig. 1 is a schematic structural view of a photodetector in embodiment 1 of the present application.
FIG. 2 is an electron micrograph (a) and an I-V pattern (b) of the tin-doped molybdenum oxide film prepared by the solution method of comparative example 1.
FIG. 3 is an I-V diagram of a tin-doped molybdenum oxide film prepared by thermal evaporation method in example 1.
Fig. 4 is an absorption spectrum of a tin-doped molybdenum oxide thin film prepared by a thermal evaporation method in example 1.
Fig. 5 is XRD patterns of the molybdenum oxide thin films (MoO 3) and tin-doped molybdenum oxide thin films (tin-doped MoO 3) prepared in comparative example 2 and example 1.
Fig. 6 is an XPS spectrum of a tin-doped molybdenum oxide thin film prepared by a thermal evaporation method in example 1.
Fig. 7 is a graph of the photo-response time of a photodetector with a tin-doped molybdenum oxide/silicon heterostructure prepared in example 1.
FIG. 8 is a graph showing the response time of the rising portion of the optical response of the photodetector fabricated without tin-doped molybdenum oxide in comparative example 2.
Fig. 9 is a response time chart of the light response rising portion of the photodetector fabricated by doping molybdenum oxide with tin in example 1.
Reference numerals: an insulating substrate 100, a tin-doped molybdenum oxide layer 110, a silicon layer 120, a first electrode 131, and a second electrode 132.
Detailed Description
The conception and the technical effects produced by the present application will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present application. It is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present application based on the embodiments of the present application.
The following detailed description of embodiments of the application is exemplary and is provided merely to illustrate the application and is not to be construed as limiting the application.
In the description of the present application, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number is understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The present application provides a photodetector having a structure as shown in fig. 1, which includes an insulating substrate 100, a first electrode 131, a second electrode 132, a tin-doped molybdenum oxide layer 110, and a silicon layer 120. Wherein the first electrode 131 and the second electrode 132 are disposed on the insulating substrate 100 at a distance from each other. The tin-doped molybdenum oxide layer 110 and the silicon layer 120 form a tin-doped molybdenum oxide/silicon heterojunction structure that connects the first electrode 131 and the second electrode 132. In some of these embodiments, the first electrode 131, the tin-doped molybdenum oxide layer 110, the silicon layer 120, and the second electrode 132 are sequentially overlapped on the insulating substrate 100. In some embodiments, the molybdenum oxide in the tin-doped molybdenum oxide layer 110 is orthorhombic molybdenum oxide (α -MoO 3), which is a two-dimensional material with a layered crystal structure, the electrical property of the intrinsic material is represented as an insulator, and by doping, such as doping of tin, a hybridization energy level is introduced into the molybdenum oxide, so that the conductivity of the molybdenum oxide can be improved by several orders of magnitude, and finally, high absorptivity of infrared light is realized. And the tin-doped molybdenum oxide layer 110 and the silicon layer 120 further form a two-dimensional material heterojunction with an ideal interface, and the tin-doped molybdenum oxide/silicon heterojunction interface can form a built-in electric field, so that the separation of photon-generated carriers is effectively promoted, and the photoelectric detector has ultra-fast response time in an infrared band. The novel working mechanism and structure of the infrared photoelectric detector provided by the photoelectric detector greatly improve the performance of the molybdenum oxide infrared detector and lay a foundation for finally realizing the high-performance infrared photoelectric detector in the future.
In some embodiments, the material of the silicon layer 120 is a multi-layer single crystal with a thickness of 30-300 nm. In some embodiments, the tin-doped molybdenum oxide of the tin-doped molybdenum oxide layer 110 is a multi-layer single crystal, with multi-layer meaning that the number of layers is greater than 2. In some of these embodiments, the number of tin-doped molybdenum oxide layers 110 is 2 to 100. It will be appreciated that during fabrication and assembly of the photodetector, the tin-doped molybdenum oxide layer 110 may further be a few-layer material that is stripped from the fabricated multi-layer single crystal. In some embodiments, the first electrode 131 and the second electrode 132 are metal electrodes, and the metal electrodes are made of at least one of gold, silver, and aluminum, and have a thickness of 50-150 nm.
The embodiment of the application also relates to a preparation method of the photoelectric detector, wherein the tin-doped molybdenum oxide layer 110 is prepared by a thermal evaporation technology. In some embodiments, the thermal evaporation comprises the steps of: the powder of molybdenum oxide and stannous salt is uniformly mixed and then evaporated onto an evaporation substrate by adopting a method of slow evaporation and then fast evaporation, wherein the evaporation speed of the slow evaporation is 0.1-0.5 nm/s, and the evaporation speed of the fast evaporation is 0.5-2 nm/s. The tin-doped molybdenum oxide obtained by vapor deposition has higher absorptivity in the infrared band by adopting a mode of combining slow vapor deposition and fast vapor deposition. In some specific embodiments, the evaporation time of the slow evaporation is 60-200 s, and the evaporation is further performed according to the speed of the slow evaporation and the fast evaporation, and the time of the fast evaporation is controlled so that the thickness of the tin-doped molybdenum oxide layer obtained after the evaporation is completed is 200-500 nm.
In some embodiments, the vapor deposited substrate is an insulating substrate including, but not limited to, alumina, silica (e.g., quartz glass), sapphire, polyethylene terephthalate (PET), etc., or a conductive substrate including, but not limited to, fluorine doped tin oxide (FTO) glass, indium Tin Oxide (ITO) glass, etc. It will be appreciated that the insulating substrate used in the evaporation substrate is also applicable to the insulating substrate 100 used in the infrared detector.
In some specific embodiments, the method for manufacturing the photodetector comprises the steps of:
Preparing a tin-doped molybdenum oxide layer by a thermal evaporation technology;
Transferring the tin-doped molybdenum oxide layer onto a silicon layer of an insulating substrate to form a tin-doped molybdenum oxide/silicon heterojunction structure;
and a first electrode and a second electrode are arranged on the surface of the tin-doped molybdenum oxide/silicon heterojunction structure.
In some embodiments, the silicon layer on the insulating substrate is obtained by Reactive Ion Etching (RIE). Wherein, the thickness of the silicon layer used for etching is 30-300 nm. The atmosphere used in the reactive ion etching can be at least one gas including trifluoromethane (CHF 3) and sulfur hexafluoride (SF 6), the etching power of the reactive ion etching is 100-350W, the gas flow of the reactive ion etching is 15-25 scm, and the etching time of the reactive ion etching is 30-90 s.
In some specific embodiments, after the tin-doped molybdenum oxide layer is prepared by thermal evaporation and evaporation, the tin-doped molybdenum oxide layer is stripped from the evaporation substrate, wherein the stripping material can be Polydimethylsiloxane (PDMS), and the stripped tin-doped molybdenum oxide layer is a few layers of tin-doped molybdenum oxide, such as 2-100 layers. And transferring the tin-doped molybdenum oxide layer to the silicon layer through a two-dimensional material transfer platform after stripping to form the tin-doped molybdenum oxide/silicon heterojunction structure. When the transfer temperature is below 25 ℃, the transfer can be easier and more convenient. In some embodiments, the first electrode and the second electrode are disposed on the surface of the tin-doped molybdenum oxide/silicon heterojunction structure by vapor deposition of electrode materials onto an insulating substrate.
Example 1
The embodiment provides a photoelectric detector, and the preparation method of the photoelectric detector is as follows:
(1) Preparation of tin-doped molybdenum oxide film
And uniformly mixing a proper amount of molybdenum oxide powder and stannous chloride powder, and placing the mixture under an evaporation substrate in a vacuum coating chamber, wherein the evaporation substrate is quartz glass. And (3) regulating the current to 50A, opening the baffle, firstly evaporating to the thickness of 10nm at a speed of 0.1-0.5 nm/s, then continuously increasing the current to about 60A, and then evaporating rapidly at a speed of 1-2 nm/s until a film with the thickness of 200-500 nm is obtained.
(2) Preparation of silicon layer
The multi-layer silicon therein is patterned by Reactive Ion Etching (RIE) on the SiO 2 -Si substrate. First try different etching atmospheres, such as: oxygen, argon, trifluoromethane, carbon tetrafluoride, sulfur hexafluoride, and the like. Finally, the atmosphere of the trifluoromethane or the sulfur hexafluoride is determined, so that the multi-layer silicon in the substrate can be etched efficiently.
The etching conditions of RIE are further optimized. Selecting a flat silicon material with the thickness range of 15-60 nm, protecting a part of the material by polymethyl methacrylate (PMMA) through an electron beam exposure process, and selecting the following parameters: CHF 3 flow 25sccm, gas pressure 2.0Pa, etching power 100W, and etching times 20s, 40s, 50s, 60s, etc. were tried, respectively. And (3) cleaning PMMA of the protection part on the material after etching, measuring steps on the surface of the etched material by an Atomic Force Microscope (AFM), and finally obtaining etching time of RIE on silicon under the condition, wherein the etching time is determined to be 40s.
RIE patterning is performed on the SiO 2 -Si substrate to form a silicon layer according to the conditions determined above.
(3) Formation of tin doped molybdenum oxide/silicon heterojunction structure
When a tin-doped molybdenum oxide layer and a silicon layer are stacked to form a heterojunction, specific temperature conditions need to be verified. The tin-doped molybdenum oxide is more easily transferred from PDMS to patterned silicon when the temperature is below 25 ℃ by testing the temperature of 15 ℃,20 ℃,40 ℃, 70 ℃ and the like.
Therefore, the tin-doped molybdenum oxide film prepared in the step (1) is taken as a tin-doped molybdenum oxide layer to be peeled off on Polydimethylsiloxane (PDMS), and then is transferred onto the silicon dioxide substrate with the silicon layer prepared in the step (2) at 20 ℃ so that the tin-doped molybdenum oxide film and the silicon layer are stacked to form a heterojunction structure.
(4) Providing a first electrode and a second electrode
And (3) evaporating metal layers with the thickness of 60nm on two sides of the silicon layer and the tin-doped molybdenum oxide layer treated in the step (3) respectively to form a first electrode and a second electrode, and finally manufacturing the photoelectric detector.
Comparative experiments and results
Comparative example 1
The comparative example provides a tin-doped molybdenum oxide film, which is different from the preparation process of the step (1) in the embodiment 1 in that the tin-doped molybdenum oxide film is prepared by adopting a solution method, and the specific steps are as follows:
S1, weighing molybdenum oxide powder, placing the molybdenum oxide powder in a quartz cup, and then placing Dan Yingzhong in a CVD tube furnace; and cleaning the silicon oxide substrate with alcohol, acetone and deionized water for three times in sequence, drying by using a nitrogen gun, placing the silicon oxide substrate into a CVD tube furnace at a position which is 15cm away from a place of a quartz cup for containing molybdenum oxide powder, introducing nitrogen into the CVD tube furnace for three times to exhaust air, and vacuumizing. Raising the temperature in the CVD tube furnace to 680 ℃ at a speed of 10 ℃/min, preserving the heat for 10min after the temperature is reached, and naturally cooling the furnace body to room temperature to produce the molybdenum oxide nano film on the silicon oxide substrate; and then stripping the film from the silicon oxide substrate to obtain the molybdenum oxide nano film.
S2, firstly preparing 50mL of tartaric acid solution with the concentration of 0.23 mol/L; and adding a proper amount of stannous chloride powder into the prepared tartaric acid solution, and slightly and uniformly stirring the solution by using a glass rod to obtain a clear and transparent intercalation solution.
And S3, heating a heating table to 50-60 ℃, placing a glass slide on the heating table, then placing the molybdenum oxide nano film prepared in the step S1 on the glass slide, dripping the intercalation solution prepared in the step S2 on the molybdenum oxide nano film by using a dropper, observing the color change of the molybdenum oxide nano film, observing once under an optical microscope every three minutes until the interface is completely green, stopping heating, and cooling to room temperature to prepare the tin-doped molybdenum oxide nano film.
Comparative example 2
This comparative example provides a photodetector whose manufacturing method is different from that of example 1 in that stannous chloride powder is not added to the vapor-deposited raw material in the preparation of the molybdenum oxide film.
The electron microscope image of the tin-doped molybdenum oxide film prepared in comparative example 1 is shown as A in FIG. 2, and it can be seen from the image that the tin doping in the molybdenum oxide prepared by the method is uneven, the tin doping amount at the 1 position is small, and the tin doping amount at the 2 position is large. B in fig. 2 and fig. 3 are I-V spectra of comparative example 1 and example 1, respectively, and black lines (dark) in fig. 2 are I-V curves of a device formed of the non-intercalated molybdenum oxide nano-film in comparative example 1, and yellow lines (light) are I-V curves of a device formed of the tin-doped molybdenum oxide nano-film after intercalation in comparative example 1; in fig. 3, the black line (dark color) is the I-V curve of the heterojunction device formed by the tin-doped molybdenum oxide nano-film in example 1, and the yellow line (light color) is the I-V curve of the non-heterojunction device formed by the tin-doped molybdenum oxide nano-film in example 1 without forming a heterojunction structure with silicon. As can be seen in conjunction with fig. 2 and 3, the non-uniform intercalation in comparative example 1 results in a small conductivity of the tin-doped molybdenum oxide, and thus a small current; in contrast, in example 1, the tin doping was more uniform due to the thermal evaporation method, and the conductivity and current of the finally produced thin film material were larger.
Fig. 4 shows the absorption spectrum of the tin-doped molybdenum oxide film prepared in example 1, and it can be seen from the graph that the tin-doped molybdenum oxide film prepared by the method has a high absorption rate in the infrared band, which is approximately more than 95%.
Fig. 5 is an XRD pattern of the molybdenum oxide thin film and the tin-doped molybdenum oxide thin film prepared in comparative example 2 and example 1, from which it can be seen that the molybdenum oxide in comparative example 2 shows strong diffraction peaks at 12.8 °, 25.7 ° and 39.04 °, corresponding to (020), (040) and (060) planes (JCPDS: 05-0508) of molybdenum oxide, respectively. After tin doping of example 1, the (0 k 0) peak is shifted to the left in the figure, demonstrating the successful insertion of Sn atoms into the crystal structure.
Fig. 6 is an XPS spectrum of the tin-doped molybdenum oxide film of example 1, from which it can be seen that after doping, the Sn 3d5/2 and 3d3/2 core levels are located at 487.44eV and 495.95eV, respectively, demonstrating that tin can effectively enter the molybdenum oxide structure.
FIG. 7 is a graph showing the light response of the photodetector prepared in example 1 under intermittent irradiation with 1550nm infrared light. Fig. 8 and 9 are graphs of the photo-response times of the photodetectors of comparative example 2 and example 1, respectively, under intermittent irradiation of 1550nm infrared light, and it can be seen from comparison of fig. 8 and 9 that the response (rise) time of the photodetector of comparative example 2, which is not doped with tin, is 17s, whereas the response (rise) time of the photodetector of the tin-doped molybdenum oxide/silicon heterojunction prepared by the above method of example 1 is 0.2s, which is considerably shortened in comparison.
From the experimental results, the tin doped molybdenum oxide/silicon heterojunction can promote the separation of photon-generated carriers, so that the detector has higher responsivity and shorter response time, and the performance of the photoelectric detector is greatly improved.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present application. Furthermore, embodiments of the application and features of the embodiments may be combined with each other without conflict.
Claims (8)
1. A photodetector, comprising:
an insulating substrate;
a first electrode and a second electrode disposed on the insulating substrate at a mutual interval;
The tin-doped molybdenum oxide/silicon heterojunction structure is connected with the first electrode and the second electrode, and is a heterojunction formed by a tin-doped molybdenum oxide layer and a silicon layer;
The silicon layer is multi-layer monocrystalline silicon, and the thickness of the silicon layer is 30-300 nm;
The tin-doped molybdenum oxide layer is a plurality of layers of single crystal tin-doped molybdenum oxide, and the number of the tin-doped molybdenum oxide layers is 2-100;
the molybdenum oxide in the tin-doped molybdenum oxide layer is orthorhombic molybdenum oxide.
2. The photodetector of claim 1 wherein said insulating substrate includes said first electrode, said silicon layer, said tin-doped molybdenum oxide layer and said second electrode in overlapping order thereon.
3. The photodetector of any one of claims 1 to 2, wherein said first electrode and said second electrode are metallic electrodes.
4. A method of manufacturing a photodetector according to any one of claims 1 to 3, wherein the tin doped molybdenum oxide layer is manufactured by thermal evaporation;
the steps of the thermal evaporation and evaporation are as follows: the method comprises the steps of uniformly mixing molybdenum oxide and stannous salt powder, and then completing evaporation by adopting a method of firstly carrying out slow evaporation and then carrying out fast evaporation, wherein the evaporation speed of the slow evaporation is 0.1-0.5 nm/s, and the evaporation speed of the fast evaporation is 0.5-2 nm/s;
the evaporation time of the slow evaporation is 60-200 s;
the thickness of the tin-doped molybdenum oxide layer obtained after the rapid evaporation is 200-500 nm.
5. The method of manufacturing according to claim 4, comprising the steps of:
Preparing a tin-doped molybdenum oxide layer by a thermal evaporation technology;
transferring the tin-doped molybdenum oxide layer onto a silicon layer of an insulating substrate to form a tin-doped molybdenum oxide/silicon heterojunction structure;
And a first electrode and a second electrode are arranged on the surface of the tin-doped molybdenum oxide/silicon heterojunction structure.
6. The method according to claim 5, wherein the silicon layer on the insulating substrate is obtained by reactive ion etching;
The reactive ion etching is carried out by adopting at least one gas containing trifluoroethane and sulfur hexafluoride;
the etching power is 100-350W;
The gas flow is 15-25 scm;
the etching time is 30-90 s.
7. The method of claim 5, wherein the transfer temperature of the tin-doped molybdenum oxide layer to the silicon layer is 25 ℃ or less.
8. The method according to any one of claims 5 to 7, wherein the method for disposing the first electrode and the second electrode on the surface of the tin-doped molybdenum oxide/silicon heterojunction structure comprises: evaporating a metal material on the insulating substrate to form the first electrode and the second electrode.
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