CN107305913B - Ultraviolet photosensitive sensor, preparation method, ultraviolet light-sensitive device and ultraviolet light detection method - Google Patents
Ultraviolet photosensitive sensor, preparation method, ultraviolet light-sensitive device and ultraviolet light detection method Download PDFInfo
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- CN107305913B CN107305913B CN201610249800.6A CN201610249800A CN107305913B CN 107305913 B CN107305913 B CN 107305913B CN 201610249800 A CN201610249800 A CN 201610249800A CN 107305913 B CN107305913 B CN 107305913B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000001514 detection method Methods 0.000 title claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 158
- 239000011787 zinc oxide Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 230000008859 change Effects 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims description 46
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- 230000000087 stabilizing effect Effects 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 239000001856 Ethyl cellulose Substances 0.000 description 10
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 10
- 229920001249 ethyl cellulose Polymers 0.000 description 10
- 235000019325 ethyl cellulose Nutrition 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000000825 ultraviolet detection Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000010329 laser etching Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
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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
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A kind of preparation method of ultraviolet photosensitive sensor, comprising: production electrode prepares zinc oxide suspension, makes zinc oxide photosensitive film, heat treatment and encapsulation.The ultraviolet photosensitive sensor prepared by this method, comprising: zinc oxide photosensitive film, for detecting ultraviolet light；First electrode and second electrode, the two are not in contact with each other, and are located at zinc oxide photosensitive film the same side, are electrical signals.A kind of ultraviolet light-sensitive device, including light-sensitive element module and signal acquisition module.A kind of ultraviolet light detection method, comprising: under light to be measured irradiation, the photo resistance of light-sensitive element module generates change in resistance and exports electric signal；The partial pressure of signal acquisition module acquisition and processing and the concatenated divider resistance output of photo resistance, according to the differential in partial pressures in adjacent fixed time period, it is determined whether refresh display.
Description
Technical Field
The invention relates to the field of sensors, in particular to an ultraviolet light sensor based on zinc oxide and a preparation method and application thereof.
Background
The zinc oxide material has a forbidden band width of 3.7eV, the material resistance only responds to ultraviolet light with the wavelength of 180nm-365nm, and does not respond to visible light and infrared light, so that the zinc oxide material is a good wide forbidden band photosensitive material. The ultraviolet sensor made of pure zinc oxide material can well avoid the interference of light rays in other wave bands except the ultraviolet wave band, thereby effectively avoiding the occurrence of false alarm.
The existing signal acquisition mode of the ultraviolet sensor is that a photosensitive material reaches a stable state under the excitation of illumination, and the difference of resistance of the photosensitive material under different illuminations represents the difference of light intensity.
On the basis of the signal acquisition mode, the existing ultraviolet photosensitive device products mainly use GaN and cold cathode tube ultraviolet sensors. The GaN-based device mainly takes GaN as a photosensitive material and takes GaN with high cost as a substrate, and meanwhile, due to the technical problem, the GaN cannot form a large-area photosensitive material, and the light receiving area of the ultraviolet device is also limited. Although avalanche type photoelectric tube products have the advantages of high sensitivity, high testing precision and the like, the avalanche type photoelectric tube products can work only under high voltage (more than 220V), and meanwhile, the avalanche type photoelectric tube has the defects of vacuum packaging, easiness in damage, large size, short service life, high cost and the like, and is not suitable for portable equipment and common environments with low requirements on testing precision. The zinc oxide product on the silicon substrate has better light response, but because silicon is a narrow forbidden band material and has response to visible light, the zinc oxide product can cause the false response of the device to light other than ultraviolet wave bands. The zinc oxide is manufactured on the insulating substrate through processes such as sputtering and the like, and the response speed is extremely low, so that the requirement of rapid test cannot be met.
In addition, no matter the zinc oxide ultraviolet sensor is manufactured on a Si substrate or other insulating substrates, because of the ultraviolet response characteristics of the zinc oxide material, the time for the photoresistance of the photosensitive material to reach the stability in the light state is very long, and the stable value is difficult to determine quickly.
Disclosure of Invention
The invention aims to provide a preparation method of an ultraviolet photosensitive sensor, the ultraviolet photosensitive sensor prepared by the method, an ultraviolet photosensitive device applying the ultraviolet photosensitive sensor and an ultraviolet detection method based on the ultraviolet photosensitive device.
In a first aspect, the present invention provides a method for preparing an ultraviolet photosensitive sensor, comprising:
(1) manufacturing an electrode: manufacturing a first electrode and a second electrode on the surface of the ITO conductive glass, wherein the first electrode and the second electrode are not contacted with each other;
(2) preparation of zinc oxide suspension: adding the binder into an organic solvent, fully dissolving to obtain a binder solution, then adding zinc oxide nano powder into the binder solution, and uniformly mixing to obtain a zinc oxide suspension;
(3) preparing a zinc oxide photosensitive film: spraying the zinc oxide suspension prepared in the step (2) on the surfaces of the first electrode and the second electrode manufactured in the step (1) to form a zinc oxide photosensitive film;
(4) and (6) performing heat treatment and packaging.
In a second aspect, the present invention provides an ultraviolet light sensitive sensor prepared by the above method, comprising: a zinc oxide photosensitive film, a first electrode and a second electrode; wherein,
the zinc oxide photosensitive film is used for detecting ultraviolet light;
the first electrode and the second electrode are not in contact with each other, are positioned on the same side of the zinc oxide photosensitive film and are used as an electric signal output end of the ultraviolet photosensitive sensor.
In a third aspect, the present invention provides an ultraviolet photosensitive device, which includes a photosensitive element module and a signal acquisition module; wherein,
the photosensitive element module is an ultraviolet photosensitive sensor prepared by the preparation method of the first aspect of the invention or an ultraviolet photosensitive sensor of the second aspect of the invention, and is used for generating resistance value change and outputting an electric signal under the illumination to be detected;
the signal acquisition module is used for acquiring and processing partial voltage output by a partial voltage resistor connected in series with the photoresistor and determining whether to refresh display or not according to a partial voltage difference value in an adjacent fixed time period;
the photosensitive element module is connected with the divider resistor in series through an extraction electrode.
In a fourth aspect, the present invention provides an ultraviolet light detection method using the above ultraviolet light sensor, including:
(1) under the irradiation of light to be detected, the photoresistor of the photosensitive element module generates resistance value change and outputs an electric signal;
(2) the signal acquisition module acquires and processes partial pressure output by a partial pressure resistor connected in series with the photoresistor, and whether to refresh display is determined according to a partial pressure difference value in an adjacent fixed time period.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the preparation method has the advantages that the zinc oxide powder is adopted as the raw material, the zinc oxide suspension is prepared in the organic solvent, and the photosensitive film is prepared by spraying the suspension on the surface of the electrode, so that the preparation method has simple process and low cost, and is suitable for large-scale industrial production.
(2) The ultraviolet photosensitive sensor takes zinc oxide as a photosensitive material, so that the interference of light in other wave bands except an ultraviolet wave band to the sensor can be effectively avoided; compared with the traditional ultraviolet photosensitive sensor, the ultraviolet photosensitive sensor disclosed by the invention can well avoid the interference of visible light, and has a good cost advantage compared with the existing GaN-based ultraviolet photosensitive sensor.
(3) The ultraviolet photosensitive device and the ultraviolet detection method based on the same overcome the defect of overlong data acquisition time caused by slow stability of a zinc oxide photoelectric resistor, and can realize stable and rapid value taking and stable characterization of ultraviolet intensity.
Drawings
FIG. 1 is a process flow diagram of a method of making an ultraviolet light sensitive sensor of the present invention;
FIG. 2 is a schematic diagram of interdigital electrodes employed in the ultraviolet light sensitive sensor of the present invention;
FIG. 3 is a schematic view of an ultraviolet light sensitive device of the present invention;
fig. 4 is a graph showing the response effect of the ultraviolet photosensor of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
In a first aspect, the present invention provides a method for preparing an ultraviolet light sensitive sensor. The preparation method is described below with reference to fig. 1.
(1) Making electrodes
And manufacturing a first electrode and a second electrode on the surface of the ITO conductive glass in a laser etching mode, wherein the first electrode and the second electrode are interdigital electrode pairs.
The purpose of manufacturing the electrodes is to enable the ultraviolet photosensitive sensor to form good ohmic contact, so that working voltage is effectively loaded at two ends of the ultraviolet photosensitive sensor, and current change of the ultraviolet photosensitive sensor to ultraviolet light is effectively output. Wherein, the distance between the first electrode and the second electrode can influence the photoresponse and the response speed of the ultraviolet photosensitive sensor, and the distance between the first electrode and the second electrode is preferably 50 microns to 500 microns, and more preferably 100 microns.
Preferably, in order to facilitate connection between the two poles of the ultraviolet photosensitive sensor and an external circuit, lead-out electrodes may be further formed on the first electrode and the second electrode, and in particular, lead-out conductive wires or conductive pins (as shown in fig. 2) may be welded or adhered to the first electrode and the second electrode. Wherein the contact resistance of the extraction electrode with the first and second electrodes affects the responsivity of the device, preferably the contact resistance is less than 0.005 ohm.
(2) Preparation of Zinc oxide suspension
Adding the binder into an organic solvent, fully dissolving to obtain a binder solution, then adding zinc oxide nano powder into the binder solution, and uniformly mixing to obtain a zinc oxide suspension. The preparation method of the present invention has no special requirements on the types of the binder and the organic solvent, and the polymeric binder, the transparent resin binder and the volatile organic solvent can be used in the preparation method of the present invention, and the skilled person can select the suitable binder and organic solvent according to the actual production requirements, and the following examples only take Ethyl Cellulose (EC) and absolute ethyl alcohol as examples for illustration. The zinc oxide nano powder and the binder are uniformly mixed, so that the effective bonding of particles in the zinc oxide photosensitive film can be realized, and the mechanical strength of the film is enhanced.
The concentration of zinc oxide and the content of the binder influence the response time of the ultraviolet photosensitive sensor. The ratio of binder to organic solvent is preferably 0.001 to 1 gram of binder: 1-50 ml of organic solvent, and more preferably 0.005 g of binder: 4 ml of organic solvent. The ratio of zinc oxide nanopowder to binder solution is preferably 0.1-2.0 grams of zinc oxide: 1-50 ml binder solution, and more preferably 1.5 g zinc oxide: 4 ml of binder solution.
(3) Making zinc oxide photosensitive film
And spraying the zinc oxide suspension onto the surfaces of the first electrode and the second electrode for 5-20 seconds to form the zinc oxide photosensitive film. The thickness of the film affects the response speed of the ultraviolet light sensor, and is preferably 100-.
(4) Thermal processing and packaging
After the zinc oxide suspension is sprayed, a heat treatment is performed to remove the organic solvent in the film, promote the curing of the binder, and improve the adhesion and stability of the device. The temperature and time of the heat treatment, which preferably ranges from 50 c to 100 c, and more preferably 75 c, affect the response speed of the ultraviolet photosensor, and the time of the heat treatment is preferably 1 minute to 30 minutes, and more preferably 5 minutes.
After the heat treatment, transparent high polymer materials are adopted for packaging, so that the device is protected, and the zinc oxide photosensitive film is prevented from being damaged by dust, moisture and external force.
In a second aspect, the invention provides an ultraviolet photosensitive sensor prepared by the method.
The ultraviolet photosensitive sensor is a substrate-free ultraviolet photosensitive sensor and comprises a zinc oxide photosensitive film, a first electrode and a second electrode. Wherein, the zinc oxide photosensitive film is used for detecting ultraviolet light; the first electrode and the second electrode are not contacted with each other and are used as an electric signal output end of the substrate-free ultraviolet photosensitive sensor.
The first electrode and the second electrode may be interdigital electrodes, which are located on the same side surface of the zinc oxide photosensitive film, and a certain distance is maintained between the electrodes, for example, 50 micrometers to 500 micrometers, and preferably 100 micrometers.
Further, in order to make it easier to connect the ultraviolet photosensor to an external circuit, extraction electrodes may be further provided on the first electrode and the second electrode, for example, extraction conductive wires or conductive pins (as shown in fig. 2) may be adhered to the electrodes.
The preparation method of the ultraviolet photosensitive sensor has the advantages of simple process and low cost, and is suitable for large-scale industrial production. The obtained ultraviolet photosensitive sensor mainly uses a zinc oxide material with a wide forbidden band, only responds to ultraviolet band light, and avoids the influence of other light except the ultraviolet band on devices. The solutions of the first and second aspects of the invention may also be extended to the application of gas-sensitive, pressure-sensitive sensors.
In a third aspect, the present invention provides an ultraviolet photosensitive device, which includes a photosensitive element module and a signal acquisition module. The photosensitive element module is used for generating resistance value change through the photosensitive material under illumination. The signal acquisition module outputs divided voltage through a divider resistor connected with the photoresistor in series, and the change of the divided voltage represents the change of the ultraviolet light intensity. The photosensitive element module is connected with the signal acquisition module through the extraction electrode. The ultraviolet photosensitive device of the present invention will be described with reference to fig. 3.
The photosensitive element module of the ultraviolet photosensitive device adopts the ultraviolet photosensitive sensor, and the photosensitive resistor generates resistance value change and outputs an electric signal under the illumination to be measured.
The signal acquisition module of the ultraviolet photosensitive device sequentially comprises a voltage stabilizing module, a partial pressure signal acquisition module, a signal processing module and a display module. The voltage stabilizing module (not shown in fig. 3) is connected to two ends of the voltage dividing resistor, and is configured to convert the divided voltage output by the voltage dividing resistor into a stable voltage, so as to reduce test differences caused by power supply fluctuations. The partial pressure signal acquisition module is connected with the voltage stabilizing module and acquires a partial pressure value after the voltage stabilizing module is subjected to stable processing through the chip. The signal processing module is connected with the partial pressure signal acquisition module and is used for calculating a partial pressure average value every fixed time period (for example, every 1/50 seconds, which can be set by a person skilled in the art according to specific requirements), and performing difference operation and comparison operation on the partial pressure average values calculated in the adjacent fixed time periods. The display module is connected with the signal processing module and used for refreshing and displaying the acquired partial pressure value in real time when the difference value operation and the comparison operation result is greater than a set value; and when the results of the difference operation and the comparison operation are less than or equal to the set value, stopping refreshing and displaying the constant voltage division value.
In a fourth aspect, the present invention provides a method for detecting ultraviolet light using the above ultraviolet light sensor. The method comprises the following steps:
firstly, under the irradiation of light to be measured, the photoresistor of the photosensitive element module generates resistance value change and outputs an electric signal.
And secondly, the signal acquisition module acquires and processes the partial pressure output by the voltage dividing resistor connected with the photoresistor in series, and whether to refresh the display is determined according to the partial pressure difference value in the adjacent fixed time period.
Specifically, the divider resistor connected in series with the photosensitive element module outputs a divided voltage, the voltage stabilizing module converts the divided voltage into a stable voltage, and generally, the voltage stabilizing module converts a 5V voltage input by the divider resistor into a 3 ± 0.01V stable voltage so as to reduce the test difference caused by power supply fluctuation. The partial pressure signal acquisition module acquires the partial pressure signal through the chip at any timeThe data acquisition frequency of the voltage division value after the stabilization processing by the voltage stabilization module is 500-1000 times/second. And then, the signal processing module performs difference operation and comparison operation on the partial pressure value acquired by the partial pressure signal acquisition module at any time, calculates a partial pressure average value every 1/50 seconds, refreshes and displays the partial pressure average value at any time, stops refreshing when the partial pressure average value is less than or equal to a set value, displays the final value by the display module, and refreshes and displays the final value by the display module until the final value is greater than the set value again. Specifically, when the difference value satisfies (V) with the set valuen+1-Vn) When M is greater than M, the display module refreshes the display result; wherein, VnIs the average value of the partial pressure at the nth/50 seconds, and n is a positive integer; m is a set value, and M is more than or equal to 0.1V and less than or equal to 0.5V, and a person skilled in the art can select a proper set value according to actual needs.
The ultraviolet photosensitive device and the ultraviolet detection method based on the same solve the problem of overlong data acquisition time caused by slow stability of the zinc oxide photoelectric resistor at present, realize stable and rapid value taking, and can represent the intensity of ultraviolet light.
The implementation of the present invention is illustrated by the following specific examples, which should be understood by those skilled in the art as not to limit the scope of the claims of the present invention. The various agents and substances used in the examples were all conventionally commercially available.
Example 1
The preparation method of the ultraviolet photosensitive sensor of the embodiment is as follows:
(1) making electrodes
An interdigital electrode pattern (as shown in fig. 2) is etched on the surface of the ITO conductive glass in a laser etching mode, the spacing between the electrodes is 300 microns, and extraction electrodes are respectively adhered to the interdigital electrodes.
(2) Preparation of Zinc oxide suspension
Dissolving 0.5 g of binder ethyl cellulose in 50 ml of absolute ethyl alcohol, and stirring until the binder ethyl cellulose is fully dissolved to obtain a binder solution; then 2 g of zinc oxide nano powder is added into the binder solution, and the mixture is stirred until the mixture is fully and uniformly mixed to obtain a zinc oxide suspension.
(3) Making zinc oxide photosensitive film
And (3) spraying the zinc oxide suspension prepared in the step (2) onto the interdigital electrode prepared in the step (1), and stopping spraying when the zinc oxide photosensitive film is 500 microns.
(4) Thermal processing and packaging
And (3) baking for 15 minutes at the temperature of 80 ℃ to remove the absolute ethyl alcohol in the film, and then packaging by using a ya kel plate and thermosol to obtain the ultraviolet photosensitive sensor.
The uv light sensitive sensor measures the current-time variation of the sensor with an electrochemical workstation (CHI660E, shanghai chen hua instrument), as shown in fig. 4.
The ultraviolet light detection is carried out by the ultraviolet light sensitive device. The signal acquisition frequency is 500 times/second, the average value of the partial pressure is calculated every 1/50 seconds, and adjacent values are subtracted in time sequence, and the set value is 0.1V, namely (V)n+1-Vn) When the voltage is less than 0.1V, the data of the display module stops refreshing and is displayed as a constant value, and the ultraviolet light intensity at the moment is represented by the value; when (V) appears againn+1-Vn) And when the voltage is more than 0.1V, the display module refreshes the display again.
The test result is stable, as shown in table 1, the partial pressure values measured at different times are averaged, and the ultraviolet light intensity to be tested can be represented through the relationship between the partial pressure value average value and the corresponding ultraviolet light intensity.
TABLE 1
Example 2
The ultraviolet light detection was performed using the ultraviolet light-sensitive device in example 1. The signal acquisition frequency is 1000 times/second, the average value of the partial pressure is calculated every 1/50 seconds, and adjacent values are subtracted in time sequence, and the set value is 0.5V, namely (V)n+1-Vn) When the voltage is less than 0.5V, the data of the display module stops refreshing and is displayed as a constant value, and the ultraviolet light intensity at the moment is represented by the value; when (V) appears againn+1-Vn) And when the voltage is more than 0.5V, the display module refreshes the display again.
The test results were stable as shown in table 2.
TABLE 2
Example 3
The preparation method of the ultraviolet photosensitive sensor of the embodiment is as follows:
(1) making electrodes
And etching an interdigital electrode pattern on the surface of the ITO conductive glass in a laser etching mode, wherein the spacing between the electrodes is 50 microns, and respectively adhering extraction electrodes on the interdigital electrodes.
(2) Preparation of Zinc oxide suspension
Dissolving 0.001 g of binder ethyl cellulose in 1 ml of absolute ethyl alcohol, and stirring until the binder ethyl cellulose is fully dissolved to obtain a binder solution; then 0.1 g of zinc oxide nano powder is added into the binder solution, and the mixture is stirred until the mixture is fully and uniformly mixed to obtain zinc oxide suspension.
(3) Making zinc oxide photosensitive film
And (3) spraying the zinc oxide suspension prepared in the step (2) onto the interdigital electrode prepared in the step (1), and stopping spraying when the zinc oxide photosensitive film is 100 microns.
(4) Thermal processing and packaging
And (3) baking for 30 minutes at the temperature of 50 ℃ to remove the absolute ethyl alcohol in the film, and then packaging by using a ya kel plate and thermosol to obtain the ultraviolet photosensitive sensor.
The method of example 1 was used to perform UV detection, and the test results were stable.
Example 4
The preparation method of the ultraviolet photosensitive sensor of the embodiment is as follows:
(1) making electrodes
And etching an interdigital electrode pattern on the surface of the ITO conductive glass in a laser etching mode, wherein the spacing between the electrodes is 500 microns, and respectively adhering extraction electrodes on the interdigital electrodes.
(2) Preparation of Zinc oxide suspension
Dissolving 1 g of binder ethyl cellulose in 50 ml of absolute ethyl alcohol, and stirring until the binder ethyl cellulose is fully dissolved to obtain a binder solution; then 2.0 g of zinc oxide nano powder is added into the binder solution, and the mixture is stirred until the mixture is fully and uniformly mixed to obtain zinc oxide suspension.
(3) Making zinc oxide photosensitive film
And (3) spraying the zinc oxide suspension prepared in the step (2) onto the interdigital electrode prepared in the step (1), and stopping spraying when the zinc oxide photosensitive film is 500 microns.
(4) Thermal processing and packaging
And (3) drying at the temperature of 100 ℃ for 5 minutes to remove the absolute ethyl alcohol in the film, and then packaging by using a ya kel plate and thermosol to obtain the ultraviolet photosensitive sensor.
The method of example 1 was used to perform UV detection, and the test results were stable.
Example 5
The preparation method of the ultraviolet photosensitive sensor of the embodiment is as follows:
(1) making electrodes
And etching an interdigital electrode pattern on the surface of the ITO conductive glass in a laser etching mode, wherein the spacing between the electrodes is 100 microns, and respectively adhering extraction electrodes on the interdigital electrodes.
(2) Preparation of Zinc oxide suspension
Dissolving 0.005 g of binder ethyl cellulose in 4 ml of absolute ethyl alcohol, and stirring until the binder ethyl cellulose is fully dissolved to obtain a binder solution; then adding 1.5 g of zinc oxide nano powder into the binder solution, and stirring until the mixture is fully and uniformly mixed to obtain a zinc oxide suspension.
(3) Making zinc oxide photosensitive film
And (3) spraying the zinc oxide suspension prepared in the step (2) onto the interdigital electrode prepared in the step (1), and stopping spraying when the zinc oxide photosensitive film is 500 microns.
(4) Thermal processing and packaging
And (3) drying at the temperature of 75 ℃ for 5 minutes to remove the absolute ethyl alcohol in the film, and then packaging by using a ya kel plate and thermosol to obtain the ultraviolet photosensitive sensor.
The method of example 1 was used to perform UV detection, and the test results were stable.
Finally, it is noted that: the above-mentioned embodiments are only examples of the present invention, and it is a matter of course that those skilled in the art can make modifications and variations to the present invention, and it is considered that the present invention is protected by the modifications and variations if they are within the scope of the claims of the present invention and their equivalents.
Claims (20)
1. A method for preparing an ultraviolet photosensitive sensor is characterized by comprising the following steps:
(1) manufacturing an electrode: manufacturing a first electrode and a second electrode on the surface of the ITO conductive glass, wherein the first electrode and the second electrode are not contacted with each other;
(2) preparation of zinc oxide suspension: adding the binder into an organic solvent, fully dissolving to obtain a binder solution, then adding zinc oxide nano powder into the binder solution, and uniformly mixing to obtain a zinc oxide suspension;
wherein the ratio of the zinc oxide nano powder to the binder solution is 0.1-2.0 g of zinc oxide: 1-50 ml binder solution; the ratio of the binder to the organic solvent is 0.001 to 1 gram of binder: 1-50 ml of organic solvent;
(3) preparing a zinc oxide photosensitive film: spraying the zinc oxide suspension prepared in the step (2) on the surfaces of the first electrode and the second electrode manufactured in the step (1) to form a zinc oxide photosensitive film;
(4) performing heat treatment and packaging;
wherein the temperature of the heat treatment is 50-100 ℃.
2. The preparation method according to claim 1, wherein extraction electrodes are respectively prepared on the first electrode and the second electrode, and then the zinc oxide suspension is sprayed on the surfaces of the first electrode and the second electrode.
3. The production method according to claim 1 or 2, wherein the first electrode and the second electrode are interdigital electrodes.
4. The production method according to claim 1 or 2, wherein a pitch between the first electrode and the second electrode is 50 to 500 μm.
5. The method of claim 4, wherein the first electrode and the second electrode are spaced apart by 100 microns.
6. The production method according to claim 1 or 2, wherein in the step (2), the ratio of the binder to the organic solvent is 0.005 g of binder: 4 ml of organic solvent.
7. The production method according to claim 1 or 2, characterized in that, in the step (2), the ratio of the zinc oxide nanopowder to the binder solution is 1.5 g of zinc oxide: 4 ml of binder solution.
8. The production method according to claim 1 or 2, wherein the thickness of the zinc oxide photosensitive film produced in step (3) is 100 to 1000 μm.
9. The method according to claim 8, wherein the thickness of the zinc oxide photosensitive film produced in step (3) is 500 μm.
10. The production method according to claim 1 or 2, wherein in the step (4), the time of the heat treatment is 1 minute to 30 minutes.
11. The production method according to claim 10, wherein in the step (4), the time of the heat treatment is 5 minutes; the temperature of the heat treatment was 75 ℃.
12. The ultraviolet light sensor prepared by the preparation method of any one of claims 1 to 11, comprising: a zinc oxide photosensitive film, a first electrode and a second electrode; wherein,
the zinc oxide photosensitive film is used for detecting ultraviolet light;
the first electrode and the second electrode are not in contact with each other, are positioned on the same side of the zinc oxide photosensitive film and are used as an electric signal output end of the ultraviolet photosensitive sensor.
13. An ultraviolet photosensitive device is characterized by comprising a photosensitive element module and a signal acquisition module; wherein,
the photosensitive element module is an ultraviolet photosensitive sensor prepared by the preparation method of any one of claims 1 to 11 or an ultraviolet photosensitive sensor of claim 12, and is used for generating resistance value change of a photosensitive resistor under illumination to be detected and outputting an electric signal;
the signal acquisition module is used for acquiring and processing partial voltage output by a partial voltage resistor connected in series with the photoresistor and determining whether to refresh display or not according to a partial voltage difference value in an adjacent fixed time period;
the photosensitive element module is connected with the divider resistor in series through an extraction electrode.
14. The ultraviolet photosensitive device of claim 13, wherein the signal acquisition module comprises a voltage stabilization module, a voltage division signal acquisition module, a signal processing module and a display module in sequence; wherein,
the voltage stabilizing module is connected with two ends of the divider resistor and is used for converting the divided voltage output by the divider resistor into stable voltage;
the voltage-dividing signal acquisition module is connected with the voltage-stabilizing module and is used for acquiring a voltage-dividing value after being stabilized by the voltage-stabilizing module;
the signal processing module is connected with the partial pressure signal acquisition module and is used for calculating a partial pressure average value every fixed time period and carrying out difference operation and comparison operation on the partial pressure average values calculated in the adjacent fixed time periods;
the display module is connected with the signal processing module and used for refreshing and displaying the acquired partial pressure value in real time when the results of the difference operation and the comparison operation are greater than a set value; and when the results of the difference operation and the comparison operation are less than or equal to the set value, stopping refreshing and displaying the constant voltage division value.
15. The ultraviolet photosensitive device of claim 14, wherein the voltage stabilizing module is configured to convert a 5V voltage output by the voltage dividing resistor into a stable voltage in a range of 2.99-3.01V.
16. The uv sensor according to claim 14 or 15, wherein the signal acquisition frequency of the voltage-dividing signal acquisition module is 500-.
17. A method of detecting ultraviolet light using the ultraviolet light sensitive device of any one of claims 13 to 16, comprising:
(1) under the irradiation of light to be detected, the photoresistor of the photosensitive element module generates resistance value change and outputs an electric signal;
(2) the signal acquisition module acquires and processes partial pressure output by a partial pressure resistor connected in series with the photoresistor, and whether to refresh display is determined according to a partial pressure difference value in an adjacent fixed time period.
18. The ultraviolet light detection method of claim 17, wherein step (2) comprises:
the voltage dividing resistor connected with the photosensitive element module in series outputs divided voltage, and the voltage stabilizing module converts the divided voltage into stable voltage;
the voltage division signal acquisition module acquires a voltage division value which is subjected to the stabilization processing by the voltage stabilization module;
the signal processing module calculates a voltage division average value every fixed time period, and performs difference operation and comparison operation on the voltage division average values calculated in the adjacent fixed time periods;
when the difference operation and the comparison operation result are larger than a set value, the display module refreshes and displays the acquired partial pressure value in real time; and when the difference operation and the comparison operation result is less than or equal to the set value, the display module stops refreshing and displays the constant voltage division value.
19. The method of claim 18, wherein the signal processing module calculates the average of the divided voltage every 1/50 seconds.
20. The ultraviolet light of claim 18 or 19The light detection method is characterized in that when the results of the difference operation and the comparison operation satisfy (V) a set valuen+1-Vn) When the voltage is larger than M, the display module refreshes and displays the acquired partial pressure value in real time;
wherein, Vn+1And VnIs the average value of partial pressure calculated in adjacent fixed time periods, and n is a positive integer; m is a set value, and M is more than or equal to 0.1V and less than or equal to 0.5V.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610249800.6A CN107305913B (en) | 2016-04-21 | 2016-04-21 | Ultraviolet photosensitive sensor, preparation method, ultraviolet light-sensitive device and ultraviolet light detection method |
| PCT/CN2016/100785 WO2017181605A1 (en) | 2016-04-21 | 2016-09-29 | Ultraviolet light sensor, method for manufacturing same, ultraviolet light device, and ultraviolet light detection method |
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| CN201610249800.6A CN107305913B (en) | 2016-04-21 | 2016-04-21 | Ultraviolet photosensitive sensor, preparation method, ultraviolet light-sensitive device and ultraviolet light detection method |
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| CN1805156A (en) * | 2006-01-13 | 2006-07-19 | 清华大学 | Photoelectric sensor based on one-dimensional semiconductor nano structure and manufacturing method thereof |
| CN101257065A (en) * | 2008-03-25 | 2008-09-03 | 浙江大学 | Method for manufacturing nanocrystalline thin-film device for ultraviolet detecting |
| CN104779314A (en) * | 2014-06-27 | 2015-07-15 | 纳米新能源（唐山）有限责任公司 | Ultraviolet photosensitive sensor based on zinc oxide and preparation method of ultraviolet photosensitive sensor |
| CN105097981A (en) * | 2015-07-01 | 2015-11-25 | 纳智源科技（唐山）有限责任公司 | Ultraviolet photosensor, manufacturing method and method for detecting ultraviolet light employing ultraviolet photosensor |
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| JP2003294527A (en) * | 2002-04-04 | 2003-10-15 | Isao Tatsuno | Film-shaped photosensor and photosensor circuit using it |
| CN204809241U (en) * | 2015-04-09 | 2015-11-25 | 纳米新能源（唐山）有限责任公司 | No basement ultraviolet photosensitive sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805156A (en) * | 2006-01-13 | 2006-07-19 | 清华大学 | Photoelectric sensor based on one-dimensional semiconductor nano structure and manufacturing method thereof |
| CN101257065A (en) * | 2008-03-25 | 2008-09-03 | 浙江大学 | Method for manufacturing nanocrystalline thin-film device for ultraviolet detecting |
| CN104779314A (en) * | 2014-06-27 | 2015-07-15 | 纳米新能源（唐山）有限责任公司 | Ultraviolet photosensitive sensor based on zinc oxide and preparation method of ultraviolet photosensitive sensor |
| CN105097981A (en) * | 2015-07-01 | 2015-11-25 | 纳智源科技（唐山）有限责任公司 | Ultraviolet photosensor, manufacturing method and method for detecting ultraviolet light employing ultraviolet photosensor |
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