CN113659034A - Photoelectric detector and preparation method and application thereof - Google Patents
Photoelectric detector and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a photoelectric detector and a preparation method and application thereof. The invention discloses a photoelectric detector which comprises a semiconductor layer and an ultraviolet absorption enhancement layer arranged on the surface of the semiconductor layer, wherein the semiconductor layer is a ZnO layer, and the ultraviolet absorption enhancement layer is Ti3C2And (3) a layer. The photoelectric detector disclosed by the invention has a high current on/off ratio, response spectra cover near ultraviolet and deep ultraviolet regions, and meanwhile, the photoelectric detector has the advantages of low cost and simple preparation process, and has wide application prospects.
Description
Technical Field
The invention relates to the technical field of detectors, in particular to a photoelectric detector and a preparation method and application thereof.
Background
The ultraviolet photodetector is a basic optoelectronic device capable of converting incident short-wave (<400nm) radiation into an electrical signal for photoelectric conversion processing. Based on the capture, identification and visualization of optical information by the detector, the ultraviolet detection technology is widely applied to the fields of military affairs, safety communication, imaging, biological detection, chemical analysis, daily life monitoring and the like. The current commercial ultraviolet photodetectors are mainly based on vacuum photomultiplier tubes and ultraviolet enhanced silicon photodetectors. With the continuous and wide application of the ultraviolet photoelectric detector, people vigorously develop related ultraviolet photoelectric detection technologies, but the ultraviolet photoelectric detector is relatively small in current on/off in a deep ultraviolet waveband (200nm-280nm), and the application of a deep ultraviolet device is limited.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. To this end, the invention proposes a photodetector capable of having a large current on/off ratio in the deep ultraviolet wavelength range.
The invention also provides a preparation method of the photoelectric detector.
The invention also provides an application of the photoelectric detector.
In a first aspect of the present invention, a photodetector is provided, which includes: the semiconductor layer is a ZnO layer, and the ultraviolet absorption enhancement layer is Ti3C2And (3) a layer.
The photoelectric detector according to the embodiment of the invention has at least the following beneficial effects: by using Ti3C2And ZnO produces a plasmon resonance effect and a self-depletion effect. Wherein the plasmon resonance effect enables the ZnO layer to characteristically absorb certain wavelengths of light. Furthermore, a ZnO layer and Ti3C2The layers form uniformly distributed local heterogeneous composite structures. In a dark state, a local built-in electric field and a depletion region appear around the heterogeneous composite structures, and the electron concentration in ZnO can be greatly reduced due to the depletion effect of the polycons, so that the effective limiterDark current of the device. The experimental results of the examples show that at 255nm, the photodetector has a high current on/off ratio.
Simultaneously, under the ultraviolet irradiation, the ZnO layer and the Ti layer3C2Excitons generated by the heterogeneous composite structure formed by the layers can be effectively separated under the action of an internal electric field, namely, the consumption of the excitons in a direct recombination mode is reduced, the photocurrent and the responsivity of the photoelectric detector can be effectively improved, and the application of a deep ultraviolet device is facilitated.
The response spectrum of the photoelectric detector covers near ultraviolet and deep ultraviolet regions, and the photoelectric detector has the advantages of low cost and simple preparation process and has wide application prospect.
In some embodiments of the invention, the ZnO layer is a ZnO three-dimensional material.
In some preferred embodiments of the present invention, the ZnO layer has a thickness of 50 to 200 nm.
In some more preferred embodiments of the present invention, the ZnO layer has a carrier concentration of 1 × 10 at 300K15～2×1018cm-3。
In some embodiments of the invention, the Ti is3C2The layer is Ti3C2A two-dimensional material.
By the above embodiment, Ti3C2Two-dimensional/three-dimensional system composed of layers and ZnO layers can trigger three-dimensional material (ZnO layer) and two-dimensional atomic layer (Ti)3C2Layer), the three-dimensional body material (ZnO layer) can show more excellent optical absorption performance, so that the photoelectric detector of the invention has good photoelectric performance in near ultraviolet region and deep ultraviolet region.
Meanwhile, the photoelectric detector adopts two-dimensional Ti3C2The material and the three-dimensional ZnO material generate a plasma resonance effect, and no complex metal deposition or sputtering process is needed, so that the surface of the semiconductor is not damaged.
In some more preferred embodiments of the invention, the Ti3C2The layer is distributed on the surface of the ZnO layer in a dispersed mode.
In some more preferred embodiments of the invention, the Ti3C2The layers are distributed in a flaky and scattered manner.
In some more preferred embodiments of the invention, the Ti3C2The sheet diameter of the layer is 0.1-10 μm.
The Ti is3C2The material is a two-dimensional material similar to thin irregular-shaped fragments, and the diameter of the fragment is Ti3C2Size of thin chips in a two-dimensional plane.
In some embodiments of the present invention, the Ti is further provided3C2And the metal contact layer is arranged on the surface of the layer and is back to one side of the ZnO layer.
In some preferred embodiments of the present invention, the metal contact layer is an Ag layer.
In some more preferred embodiments of the present invention, the Ag layer is an Ag interdigitated electrode.
With the above embodiment, Ag interdigital electrodes are used for transmitting light and dark current.
In some embodiments of the present invention, a substrate is further included, and the semiconductor layer is disposed on the substrate.
In some preferred embodiments of the present invention, the substrate is quartz.
In a second aspect of the present invention, a method for manufacturing the above-mentioned photodetector is provided, including the following steps:
s1, coating the ZnO colloidal solution on the substrate, and annealing to form a ZnO layer;
s2, adding Ti3C2Dropping the solution on the ZnO layer, drying to form Ti3C2And (3) a layer.
The preparation method of the photoelectric detector provided by the embodiment of the invention at least has the following beneficial effects:
the invention adopts Ti3C2The material is used as an ultraviolet absorption enhancement layer of the photoelectric detector, so that the deep ultraviolet absorption of the ZnO material is enhanced, and the deep ultraviolet detection performance of the photoelectric detector is enhanced; photoelectric detectorThe measuring device adopts Ti3C2The material and the ZnO material generate a plasma resonance effect, and no complex metal deposition or sputtering process is needed, so that the surface of the semiconductor is not damaged; the response spectrum of the photoelectric detector prepared by the invention covers near ultraviolet and deep ultraviolet regions, and the photoelectric detector has the advantages of low cost and simple preparation process and has wide application prospect.
In some embodiments of the present invention, the method further comprises step S3, at Ti3C2A metal contact layer is prepared on the layer.
In some preferred embodiments of the present invention, in step S3, Ti3C2Preparing Ag interdigital electrodes on the layer.
In some more preferred embodiments of the present invention, in step S3, Ti3C2And thermally evaporating the layer to prepare the Ag interdigital electrode.
In some embodiments of the present invention, the substrate is washed and hydrophilically treated before applying the ZnO colloid solution to the substrate in step S1.
In some preferred embodiments of the present invention, in step S1, the washing process is to wash the substrate with acetone, ethanol, and water in sequence.
In some preferred embodiments of the present invention, in step S1, the hydrophilic treatment process is irradiating ultraviolet light to the upper surface of the washed substrate.
In some more preferred embodiments of the present invention, in step S1, the ultraviolet light irradiation time is 10 to 20 min.
In some more preferred embodiments of the present invention, in step S1, the ultraviolet light irradiation time is 15 min.
In some embodiments of the present invention, a ZnO colloidal solution is spin-coated on the upper surface of the substrate in step S1.
In some preferred embodiments of the present invention, the ZnO colloidal solution is spin-coated at 1000-3000rpm for 10-30 s.
In some more preferred embodiments of the present invention, the ZnO colloid solution is spin coated at 2000rpm for 20 s.
In some embodiments of the present invention, in step S1, the ZnO layer is annealed at 400 ℃ + 500 ℃ in an air atmosphere.
In some preferred embodiments of the present invention, in step S1, the annealing is performed at an initial temperature of 10 to 50 ℃, a temperature rising rate of 2 to 8 ℃/min, and a holding time of 1.5 to 3 hours.
In some more preferred embodiments of the present invention, in step S1, the annealing is performed at an initial temperature of 30 ℃, a temperature rising rate of 5 ℃/min, and a holding time of 2 hours.
In some embodiments of the present invention, in step S1, preparation of the ZnO colloidal solution: adding zinc acetate and PVA into an ethanol water solution, stirring for the first time to obtain a mixed solution (I), adding acetic acid into the mixed solution (I), stirring for the second time to obtain a mixed solution (II), and standing the mixed solution (II) to obtain a ZnO colloidal solution.
In some preferred embodiments of the present invention, in the preparation of the ZnO colloid solution, the ethanol aqueous solution is prepared with ethanol and water in a volume ratio of 1:1 to 1: 15.
In some more preferred embodiments of the present invention, in the preparation of the ZnO colloid solution, the ethanol aqueous solution is prepared with ethanol and water in a volume ratio of 1: 9.
In some preferred embodiments of the present invention, in the preparation of the ZnO colloidal solution, the first stirring rotation speed is 300-700rpm, and the stirring time is 0.2-0.8 h.
In some more preferred embodiments of the present invention, in the preparation of the ZnO colloid solution, the first stirring rotation speed is 500rpm, and the stirring time is 0.5 h.
In some preferred embodiments of the present invention, in the preparation of the ZnO colloidal solution, the second stirring rotation speed is 300-700rpm, and the stirring time is 3-9 h.
In some more preferred embodiments of the present invention, in the preparation of the ZnO colloidal solution, the second stirring rotation speed is 500rpm, and the stirring time is 6 hours.
In some preferred embodiments of the present invention, acetic acid is added dropwise to the mixed solution (i) in the preparation of the ZnO colloid solution.
In some embodiments of the invention, in step S2, the Ti3C2The solution is Ti3C2Ethanol solution (I).
In some preferred embodiments of the present invention, in step S2, the Ti3C2The ethanol solution (i) was centrifuged and diluted before drop coating.
In some more preferred embodiments of the present invention, in step S2, Ti3C2And centrifuging the ethanol solution (II) to obtain a supernatant.
In some more preferred embodiments of the present invention, in step S2, Ti3C2Centrifugation conditions of ethanol solution (ii): 2000 and 5000rpm for 15-25 min.
In some more preferred embodiments of the present invention, in step S2, Ti3C2Centrifugation conditions of ethanol solution (ii): 3500rpm, 20 min.
In some more preferred embodiments of the present invention, in step S2, the diluting is to add ethanol to the supernatant to prepare Ti3C2Ethanol solution (I).
In some more preferred embodiments of the present invention, the volume ratio of the supernatant to ethanol during the dilution of the supernatant in step S2 is 1:1 to 1: 15.
In some more preferred embodiments of the present invention, the volume ratio of the supernatant to ethanol during the dilution of the supernatant in step S2 is 1:4 to 1: 9.
In some more preferred embodiments of the present invention, during the dilution of the supernatant in step S2, the volume ratio of the supernatant to ethanol is 1: 9.
In some more preferred embodiments of the present invention, in step S2, the Ti3C2The pH value of the ethanol solution (I) is 5.5-6.5.
In some preferred embodiments of the present invention, the Ti is3C2And storing the ethanol solution (I) in an inert gas atmosphere for later use.
In some more preferred embodiments of the invention, the Ti is3C2The ethanol solution (I) was stored under argon atmosphere for further use.
In a third aspect of the present invention, an application of the above-mentioned photodetector in the field of photodetection technology is provided. Has the advantages that:
the photoelectric detector disclosed by the invention adopts two-dimensional Ti3C2The material is used as an ultraviolet absorption enhancement layer, so that the deep ultraviolet absorption of the ZnO material is enhanced, and the deep ultraviolet detection performance of the photoelectric detector is enhanced;
the photoelectric detector disclosed by the invention adopts two-dimensional Ti3C2The material and the three-dimensional ZnO material generate a plasma resonance effect, and no complex metal deposition or sputtering process is needed, so that the surface of the semiconductor is not damaged;
the response spectrum of the photoelectric detector disclosed by the invention covers near ultraviolet and deep ultraviolet regions, and meanwhile, the photoelectric detector has the advantages of low cost and simple preparation process and has wide application prospect.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic structural diagram of a photodetector according to an embodiment of the present invention;
FIG. 2 is a graph of current-voltage curves of a photodetector made in accordance with an embodiment of the present invention in the dark state and under UV light;
FIG. 3 is a diagram of a photo-switch of a photodetector made in accordance with an embodiment of the present invention at 255 nm;
fig. 4 is a graph of the ultraviolet response characteristic of the photodetector manufactured in the embodiment of the present invention.
Reference numerals: substrate 100, ZnO layer 200, Ti3C2Layer 300, metal contact layer 400.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it should be understood that the orientation or positional relationship referred to in the description of the orientation, such as the upper, lower, front, rear, left, right, etc., is based on the orientation or positional relationship shown in the drawings, and is only for convenience of description and simplification of description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present numbers, and the above, below, within, etc. are understood as including the present numbers. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood 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 invention, unless otherwise explicitly limited, terms such as arrangement, installation, connection and the like should be understood in a broad sense, and those skilled in the art can reasonably determine the specific meanings of the above terms in the present invention in combination with the specific contents of the technical solutions.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means 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 invention. In this specification, the schematic representations of the terms used above do not necessarily 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.
Example 1
A photodetector, as shown in fig. 1: comprises a substrate 100 and a first electrode disposed on the substrate 100And an ultraviolet absorption enhancing layer disposed on the upper surface of the semiconductor layer. The substrate 100 is quartz, the semiconductor layer is a ZnO layer 200, and the ultraviolet absorption enhancement layer is Ti3C2Layer 300. The ZnO layer 200 is a ZnO three-dimensional material, the thickness of the ZnO layer 200 is 50-200nm, and the carrier concentration of the ZnO layer 200 at 300K is 1 × 1015～2×1018cm-3。Ti3C2Layer 300 is Ti3C2Two-dimensional material, Ti3C2Layer 300 is dispersedly distributed on the surface of the ZnO layer 200, Ti3C2The layer 300 is dispersed in a sheet form having a diameter of 0.1-10 μm. The photoelectric detector also comprises a photoelectric detector arranged on Ti3C2A metal contact layer 400 on the surface of layer 300 and facing away from the side of ZnO layer 200. The metal contact layer 400 is an Ag layer, and the Ag layer is an Ag interdigital electrode.
The embodiment prepares the above photodetector, and the specific process is as follows:
and (I) ultrasonic washing the quartz substrate by using acetone, ethanol and deionized water in sequence, wherein the ultrasonic power is 240W, and the ultrasonic time is 15min respectively, so as to remove organic matters and oxide layers on the surface. Irradiating the upper surface of the substrate with ultraviolet light having ultraviolet wavelengths of 185nm and 254nm and ultraviolet radiation intensity of about 100 μ w/cm for a hydrophilic treatment time of 15min before spin-coating the ZnO colloidal solution2。
(II) adding 1.44g of zinc acetate and 0.75g of PVA (viscous catalyst) into a beaker containing 1mL of ethanol and 9mL of deionized water, placing the beaker on a magnetic stirrer to stir (500rpm) for half an hour to obtain a mixed solution (I), dropwise adding 0.5mL of acetic acid into the mixed solution (I) in the beaker, continuing stirring for 6 hours to obtain a mixed solution (II), and placing the mixed solution (II) in a refrigerator overnight to obtain the ZnO colloidal solution. And (3) taking 30 mu L of prepared ZnO colloidal solution to spin coat (2000rpm, 20s) on the upper surface of the quartz substrate subjected to hydrophilic treatment, then placing the quartz substrate spin-coated with the ZnO colloidal solution in a high-temperature tube furnace, annealing at 450 ℃ in air atmosphere, wherein the initial temperature is 30 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to form the ZnO layer. Wherein the room temperature is 25 ℃.
(III) adding Ti at a concentration of 2mg/mL3C2The ethanol solution (II) was centrifuged (3500rpm, 20min), and then the supernatant was taken out. Diluting with anhydrous ethanol at a volume ratio of 1:9 (i.e., the volume of the supernatant: the volume of anhydrous ethanol is 1: 9) to obtain diluted Ti3C2Controlling the pH value of the ethanol solution (I) to be 5.5-6.5. To protect the Ti produced3C2Ethanol solution (I) for Ti prevention3C2Oxidizing the ethanol solution (I) to obtain Ti3C2The ethanol solution (I) was stored in an argon-filled storage bottle and placed in a refrigerator at a temperature of 5 ℃ for further use.
(IV) taking 10 mu L of diluted Ti3C2Dripping ethanol solution (I) on the upper surface of the ZnO layer, and naturally drying to form Ti3C2And (3) a layer.
(V) finally at Ti3C2And thermally evaporating the relative position of the upper surface of the layer to prepare an Ag interdigital electrode, forming a metal contact layer, and preparing the photoelectric detector. Wherein the pressure in the evaporation chamber is 5 × 10-4Pa, the evaporation speed is 0.3 angstrom per second, and the thickness of the prepared Ag interdigital electrode is 100 nm.
Example 2
The embodiment prepares a photoelectric detector, and the specific process is as follows:
and (I) ultrasonic washing the quartz substrate by using acetone, ethanol and deionized water in sequence, wherein the ultrasonic power is 240W, and the ultrasonic time is 15min respectively, so as to remove organic matters and oxide layers on the surface. Irradiating the upper surface of the substrate with ultraviolet light having ultraviolet wavelengths of 185nm and 254nm and ultraviolet radiation intensity of about 100 μ w/cm for a hydrophilic treatment time of 15min before spin-coating the ZnO colloidal solution2。
(II) adding 1.44g of zinc acetate and 0.75g of PVA (viscous catalyst) into a beaker containing 1mL of ethanol and 9mL of deionized water, placing the beaker on a magnetic stirrer to stir (500rpm) for half an hour to obtain a mixed solution (I), dropwise adding 0.5mL of acetic acid into the mixed solution (I) in the beaker, continuing stirring for 6 hours to obtain a mixed solution (II), and placing the mixed solution (II) in a refrigerator overnight to obtain the ZnO colloidal solution. And (3) taking 30 mu L of prepared ZnO colloidal solution to spin coat (2000rpm, 20s) on the upper surface of the quartz substrate subjected to hydrophilic treatment, then placing the quartz substrate spin-coated with the ZnO colloidal solution in a high-temperature tube furnace, annealing at 450 ℃ in air atmosphere, wherein the initial temperature is 30 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to form the ZnO layer. Wherein the room temperature is 25 ℃.
(III) adding Ti at a concentration of 2mg/mL3C2The ethanol solution (II) was centrifuged (3500rpm, 20min), and then the supernatant was taken out. Diluting with anhydrous ethanol at a volume ratio of 1:4 (i.e., the volume of the supernatant: the volume of anhydrous ethanol is 1: 4) to obtain diluted Ti3C2Controlling the pH value of the ethanol solution (I) to be 5.5-6.5. To protect the Ti produced3C2Ethanol solution (I) for Ti prevention3C2Oxidizing the ethanol solution (I) to obtain Ti3C2The ethanol solution (I) was stored in an argon-filled storage bottle and placed in a refrigerator at a temperature of 5 ℃ for further use.
(IV) taking 10 mu L of diluted Ti3C2Dripping ethanol solution (I) on the upper surface of the ZnO layer, and naturally drying to form Ti3C2And (3) a layer.
(V) finally at Ti3C2And thermally evaporating the relative position of the upper surface of the layer to prepare an Ag interdigital electrode, forming a metal contact layer, and preparing the photoelectric detector. Wherein the pressure in the evaporation chamber is 5 × 10-4Pa, the evaporation speed is 0.3 angstrom per second, and the thickness of the prepared Ag interdigital electrode is 100 nm.
Test examples
This test example tested the performance of the photodetector prepared in example 1. Wherein:
the dark current of the photodetector under the irradiation of ultraviolet light of 255nm and 368nm in a dark place is measured, and the measurement result is shown in fig. 2, wherein in fig. 2, the abscissa is voltage and the ordinate is current.
The current regulation capability of the photoelectric detector is tested, the illumination and dark current of the photoelectric detector are tested under 255nm, and the test result is shown in fig. 3.
The ultraviolet response characteristics of the prepared photodetector were tested, and the test results are shown in fig. 4 under a bias of 5V, in fig. 4, the abscissa is the wavelength and the ordinate is the intensity, which have been normalized.
As can be seen from FIG. 2, the dark current ratio of the prepared photodetector reaches 10 under the irradiation of 255nm deep ultraviolet light2。
As can be seen from fig. 3, the fabricated photodetector has a high current on-off ratio.
As can be seen from FIG. 4, the responsivity has a peak at 255nm and 368nm of the ultraviolet region, wherein 255nm belongs to the deep ultraviolet region, which indicates that the prepared photoelectric detector has deep ultraviolet photoelectric detection performance.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A photodetector, comprising: the semiconductor layer is a ZnO layer, and the ultraviolet absorption enhancement layer is Ti3C2And (3) a layer.
2. The photodetector of claim 1, wherein the ZnO layer is a ZnO three-dimensional material, and the Ti layer is Ti3C2The layer is Ti3C2A two-dimensional material.
3. The photodetector of claim 1, wherein said Ti3C2The layer is distributed on the surface of the ZnO layer in a dispersed mode.
4. A photodetector according to claim 3 characterised in that said Ti is3C2The layers are dispersed and distributed in a sheet shape, and the sheet diameter is 0.1-10 mu m.
5. The photodetector of claim 1, further comprising a layer disposed on said Ti3C2And the metal contact layer is arranged on the surface of the layer and is back to one side of the ZnO layer.
6. The photodetector of claim 5, wherein the metal contact layer is an Ag layer, and the Ag layer is an Ag interdigital electrode.
7. The photodetector of claim 1, further comprising a substrate, wherein said semiconductor layer is disposed on said substrate.
8. A photodetector according to claim 7, characterised in that the substrate is quartz.
9. A method for manufacturing a photodetector is characterized by comprising the following steps:
s1, coating the ZnO colloidal solution on the substrate, and annealing to form a ZnO layer;
s2, adding Ti3C2Dropping the solution on the ZnO layer, drying to form Ti3C2And (3) a layer.
10. The application of the photoelectric detector according to any one of claims 1 to 8 or the photoelectric detector prepared by the preparation method according to claim 9 in the technical field of photoelectric detection.
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