CN111244201A - Flexible self-supporting ZnO ultraviolet detector and preparation method thereof - Google Patents

Flexible self-supporting ZnO ultraviolet detector and preparation method thereof Download PDF

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CN111244201A
CN111244201A CN202010039582.XA CN202010039582A CN111244201A CN 111244201 A CN111244201 A CN 111244201A CN 202010039582 A CN202010039582 A CN 202010039582A CN 111244201 A CN111244201 A CN 111244201A
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ultraviolet detector
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CN111244201B (en
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刘可为
郑智遥
陈星�
申德振
张振中
李炳辉
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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    • HELECTRICITY
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    • H01L31/00Semiconductor 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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Abstract

The invention provides a flexible self-supporting ZnO ultraviolet detector, which belongs to the technical field of ultraviolet detection and comprises the following components: the flexible ZnO nano-structure comprises a quadruped ZnO nano-structure layer, two electrodes arranged on the surface of the quadruped ZnO nano-structure layer and a flexible substrate; the quadruped ZnO nanostructure layer independently exists to realize self-supporting and is arranged on the flexible substrate through transfer. The invention also provides a preparation method of the flexible self-supporting ZnO ultraviolet detector. The ultraviolet detector adopts a four-footed ZnO nano-structure layer, has a special four-footed structure, takes four nanowires as a unit, and is stacked into a flocculent self-supporting structure, so that the flexible ultraviolet detector with high response speed is obtained simply and efficiently; the quadruped ZnO nano-structure layer has high crystallization quality, excellent performance, high light-dark rejection ratio and high response speed, can be applied to the manufacture of a flexible ultraviolet detector, and effectively solves the problem that the substrate in the conventional ZnO micro-nano structure flexible ultraviolet detector cannot resist high temperature.

Description

Flexible self-supporting ZnO ultraviolet detector and preparation method thereof
Technical Field
The invention relates to the technical field of ultraviolet detection, in particular to a flexible self-supporting ZnO ultraviolet detector and a preparation method thereof.
Background
The ultraviolet detection technology is a dual-purpose detection technology for military and civil use, which is developed after laser and infrared detection technologies, and the modern ultraviolet detection technology is a precise detection system which integrates multiple subjects such as an ultraviolet detector, optical design, micro machining, an integrated circuit and the like. Because of the advantages of low false alarm rate, good concealment, strong anti-electromagnetic interference capability and the like, the method is widely applied to the fields of sewage purification ultraviolet detection, fire monitoring, missile early warning, ultraviolet communication, ozone hole detection and the like. In recent years, wide bandgap semiconductor ultraviolet detectors are considered to be third generation ultraviolet detectors that can replace vacuum photomultipliers and Si photomultipliers due to their advantages of small size, light weight, no need for filters during operation, no need for refrigeration, etc. Among a plurality of wide bandgap semiconductor materials, a ZnO-based material has the advantages of low defect density, strong radiation resistance, environmental friendliness and the like, the optical band gap of the ZnO-based material can be continuously adjusted within the range of 3.37-7.78eV by doping Mg, meanwhile, ZnO has a typical hexagonal-wurtzite crystal structure, different one-dimensional micro-nano structures can be very easily grown, and the existence of various defects further enables the ZnO nano structure to become one of the most ideal materials for photoelectric detection and advanced photoelectron/luminescence technology.
The traditional ZnO ultraviolet detector mainly takes sapphire, silicon wafers or quartz as a substrate, and cannot be bent and is not easy to transfer. The substrate used by the flexible ultraviolet detector with the ZnO micro-nano structure is not high-temperature resistant, most of the materials can bear the temperature limit of 150-200 ℃, and the materials cannot be directly prepared on the flexible substrate, so that the preparation of flexible devices is limited. In view of this, research on a flexible self-supporting ZnO ultraviolet detector and a preparation method thereof is urgently needed, and the technical problem that a flexible substrate of the conventional ZnO micro-nano structure flexible ultraviolet detector is not high-temperature-resistant is solved.
Disclosure of Invention
The invention aims to provide a flexible self-supporting ZnO ultraviolet detector and a preparation method thereof aiming at the defects of the prior art, the flexible self-supporting ZnO ultraviolet detector adopts a four-footed ZnO nano-structure layer which has a special four-footed structure, four nanowires are taken as a unit and are stacked into a flocculent self-supporting structure, the four-footed ZnO nano-structure layer has high crystallization quality, excellent performance, high light-dark inhibition ratio and high response speed, can be applied to the manufacture of the flexible ultraviolet detector, and effectively solves the problem that the substrate in the existing ZnO micro-nano structure flexible ultraviolet detector cannot resist high temperature.
The object of the invention can be achieved by the following technical measures:
the invention provides a flexible self-supporting ZnO ultraviolet detector, which comprises:
the flexible ZnO nano-structure comprises a quadruped ZnO nano-structure layer, two electrodes arranged on the surface of the quadruped ZnO nano-structure layer and a flexible substrate;
the quadruped ZnO nanostructure layer independently exists to realize self-supporting and is arranged on the flexible substrate through transfer.
Further, the thickness of the quadruped ZnO nano-structure layer is 50-1000 microns; wherein the diameter of each four-foot of the four-foot ZnO nano structure is 50-100 nm, and the length of each four-foot is 2-5 mu m.
Further, the two electrodes are independently designed and independently selected from any one of an In electrode, an Au electrode, an Ag electrode or an Al electrode, and the thickness of the electrodes is 30-50 nm.
Furthermore, the two electrodes are both circular electrodes, and the diameter of each electrode is 1-2 mm; the distance between the two electrodes is less than or equal to 1 mm.
Further, the flexible substrate is a polyethylene terephthalate substrate or a woven fabric substrate.
The invention also provides a preparation method of the flexible self-supporting ZnO ultraviolet detector, which comprises the following steps:
s1: preparing the quadruped ZnO nanostructure layer;
s2: fixing the two electrodes on the quadruped ZnO nanostructure layer in a bonding mode;
s3: and transferring the quadruped ZnO nano-structure layer bonded with the two electrodes onto the flexible substrate, compacting and fixing, and paving parchment paper before compacting to prevent the quadruped ZnO nano-structure layer from being damaged and stained in the compacting process, thereby obtaining the flexible self-supporting ZnO ultraviolet detector.
Further, the method for preparing the quadruped-shaped ZnO nanostructure layer in step S1 is any one of a flame transport method, a chemical vapor deposition method, and a hydrothermal method.
Further, in the step S1, the chemical vapor deposition method is adopted to prepare the quadruped ZnO nanostructure layer, and the preparation steps are as follows:
s10: grinding and uniformly mixing ZnO powder and graphite powder according to the mass ratio of 1:1, and then placing the mixture in chemical vapor deposition equipment to be used as a growth source;
s11: heating the chemical vapor deposition equipment under the protection of inert gas, wherein the heating control parameters are as follows: (50 +/-1) min is increased from room temperature to 1000 ℃, and (30 +/-1) min is increased from 1000 ℃ to 1130-1150 ℃; when the temperature rises to 1000 ℃, introducing oxygen, and controlling the flow of the oxygen to be 15-20 sccm;
s12: preserving the heat at 1130-1150 deg.c for 60 +/-1 min for growing and depositing four-footed ZnO nanometer structure;
s13: and after the deposition is finished, cooling to room temperature, and directly separating and taking out the ZnO nano-structure layer with tweezers to obtain the quadruped ZnO nano-structure layer.
Further, the inert gas is argon or nitrogen.
Further, the inert gas is argon, and the flow of the argon is 90-110 sccm.
The flexible self-supporting ZnO ultraviolet detector adopts the quadruped ZnO nano-structure layer, has a special quadruped structure, takes four nanowires as a unit, each structure unit is tightly connected, the structure is relatively firm, the quadruped ZnO nano-structure layer can be separated from a substrate to independently exist when the thickness is large enough, and the quadruped ZnO nano-structure layer can be stacked into a flocculent self-supporting structure, so that more possibilities are provided for the selection of the substrate of the flexible ultraviolet detector, and the problem that the substrate in the existing ZnO micro-nano structure flexible ultraviolet detector cannot resist high temperature is effectively solved; the four-footed ZnO nanostructure layer has high crystallization quality, excellent performance, high light-dark inhibition ratio and high response speed, can be transferred to a flexible substrate, and can simply and efficiently obtain a flexible ultraviolet detector with high response speed. The preparation method of the flexible self-supporting ZnO ultraviolet detector is simple and efficient, the preparation process of the four-footed ZnO nano-structure layer is controllable and can be designed, and the thickness of the four-footed ZnO nano-structure layer can be designed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a flexible self-supporting ZnO ultraviolet detector of the invention;
FIG. 2 is a schematic structural diagram of the flexible self-supporting ZnO ultraviolet detector in a bending state;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a quadruped ZnO nanostructure in one embodiment of the invention;
FIG. 4 is a voltage-current (I-V) characteristic curve of a flexible self-supporting ZnO ultraviolet detector in a dark state and under 365nm illumination according to an embodiment of the invention;
FIG. 5 is a voltage-current (I-V) characteristic curve of a flexible self-supporting ZnO ultraviolet detector in a bending state under a dark state and under 365nm illumination;
fig. 6 is a comparison of fig. 4 and 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In order to make the description of the present disclosure more complete and complete, the following description is given for illustrative purposes with respect to the embodiments and examples of the present invention; it is not intended to be the only form in which the embodiments of the invention may be practiced or utilized. The embodiments are intended to cover the features of the various embodiments as well as the method steps and sequences for constructing and operating the embodiments. However, other embodiments may be utilized to achieve the same or equivalent functions and step sequences.
The invention provides a flexible self-supporting ZnO ultraviolet detector, as shown in figures 1 and 2, comprising:
the flexible ZnO nano-structure comprises a quadruped ZnO nano-structure layer, two electrodes arranged on the surface of the quadruped ZnO nano-structure layer and a flexible substrate;
the quadruped ZnO nanostructure layer independently exists to realize self-supporting and is arranged on the flexible substrate through transfer.
Wherein the quadruped ZnO nano structure has a special quadruped structure, four nanowires are taken as a structural unit, the diameter of each quadruped is 50-100 nm, and the length of each quadruped is 2-5 mu m. Each structural unit is tightly connected, the structure is relatively firm, when the thickness is large enough, the structural units can be separated from the substrate and independently exist, and the structural units are stacked into a flocculent self-supporting structure, namely a four-footed ZnO nano-structure layer, and the thickness is 50-1000 microns.
Wherein, the two electrodes are independently designed, and the electrodes for the ultraviolet detector known by the technicians in the field can be adopted. Preferably, the two electrodes are independently selected from any one of an In electrode, an Au electrode, an Ag electrode or an Al electrode; the thickness of the electrode is preferably 30 to 50nm, more preferably 35 to 45nm, and most preferably 40 nm. The shape of the two electrodes is preferably circular, and the diameter is preferably 1-2 mm, more preferably 1.2-1.8 mm, and most preferably 1.5 mm. The distance between the two electrodes is preferably less than or equal to 1mm, more preferably 0.2-1 mm, and most preferably 0.5 mm.
Because the quadruped ZnO nanostructure layer can be self-supporting, the quadruped ZnO nanostructure layer can be directly taken up and transferred onto any substrate, and more possibilities are provided for the selection of the substrate of the flexible ultraviolet detector, and preferably, the flexible substrate is a polyethylene terephthalate substrate or a woven fabric substrate.
The invention also provides a preparation method of the flexible self-supporting ZnO ultraviolet detector, which comprises the following steps:
s1: preparing the quadruped ZnO nanostructure layer;
s2: fixing the two electrodes on the quadruped ZnO nanostructure layer in a bonding mode;
s3: and transferring the quadruped ZnO nano-structure layer bonded with the two electrodes onto the flexible substrate, compacting and fixing, and paving parchment paper before compacting to prevent the quadruped ZnO nano-structure layer from being damaged and stained in the compacting process, thereby obtaining the flexible self-supporting ZnO ultraviolet detector.
The method for preparing the quadruped ZnO nanostructure layer in the step S1 is any one of a flame transport method, a chemical vapor deposition method and a hydrothermal method. When the quadruped ZnO nano-structure layer is prepared by adopting a chemical vapor deposition method, the preparation steps are as follows:
s10: grinding and uniformly mixing ZnO powder and graphite powder according to the mass ratio of 1:1, and then placing the mixture in chemical vapor deposition equipment to be used as a growth source;
s11: heating the chemical vapor deposition equipment under the protection of inert gas, wherein the heating control parameters are as follows: (50 +/-1) min is increased from room temperature to 1000 ℃, and (30 +/-1) min is increased from 1000 ℃ to 1130-1150 ℃; when the temperature rises to 1000 ℃, introducing oxygen, and controlling the flow of the oxygen to be 15-20 sccm;
s12: preserving the heat at 1130-1150 deg.c for 60 +/-1 min for growing and depositing four-footed ZnO nanometer structure;
s13: and after the deposition is finished, cooling to room temperature, and directly separating and taking out the ZnO nano-structure layer with tweezers to obtain the quadruped ZnO nano-structure layer.
Wherein, the inert gas can be selected to be argon or nitrogen. When the inert gas is argon, the flow rate of the argon is preferably 90-110 sccm.
Example 1
The preparation method of the flexible self-supporting ZnO ultraviolet detector provided by the embodiment of the invention comprises the following steps:
s1: the preparation method of the quadruped ZnO nanostructure layer comprises the following specific steps:
s10: grinding and uniformly mixing ZnO powder and graphite powder according to the mass ratio of 1:1, and then placing the mixture in chemical vapor deposition equipment to be used as a growth source;
s11: heating the chemical vapor deposition equipment under the protection of argon, wherein the heating control parameters are as follows: 50min from room temperature to 1000 deg.C, 30min from 1000 deg.C to 1150 deg.C; when the temperature rises to about 1000 ℃, introducing oxygen, and controlling the flow of the oxygen to be 16 sccm;
s12: keeping the temperature at 1150 ℃ for 60min for growing and depositing a quadruped ZnO nano structure;
s13: and after the deposition is finished, cooling to room temperature, and directly separating and taking out the four-footed ZnO nanostructure layer with the thickness of 50 mu m by using tweezers.
S2: fixing the two electrodes on the quadruped ZnO nanostructure layer in a bonding mode; the two electrodes are round In particle electrodes, the diameter of the round In particle electrodes is 1.5mm, the thickness of the round In particle electrodes is 40nm, and the distance between the two electrodes is 0.5 mm.
S3: and transferring the quadruped ZnO nanostructure layer bonded with the two electrodes onto a polyethylene terephthalate flexible substrate, compacting and fixing, and paving parchment paper before compacting to prevent the quadruped ZnO nanostructure layer from being damaged and stained in the compacting process, thereby obtaining the flexible self-supporting ZnO ultraviolet detector.
A Scanning Electron Microscope (SEM) photograph of the quadruped ZnO nanostructure layer prepared in this example is shown in fig. 3, in which the diameter of the quadruped is 50nm and the length of the quadruped is 3 μm.
And (3) performance testing:
1) the flexible self-supporting ZnO ultraviolet detector prepared in this example in a flat state was subjected to a voltage-current (I-V) characteristic curve test in a dark state and under 365nm illumination, and the specific test method was:
the Agilent B1500 type semiconductor analyzer device was used to perform voltage-current performance tests on the flexible self-supporting ZnO uv detector of this example in dark and light states. Firstly, connecting two electrodes of the flexible self-supporting ZnO ultraviolet detector prepared in the embodiment with a semiconductor analyzer by using a probe station, after the connection between the apparatus and the device is finished, standing the device and the whole system in a dark state for 30 minutes, and then testing. The voltage output is set to-15V to +15V, the sampling interval is 100mV, and the obtained data is an I-V characteristic diagram of the device in a dark state. And then irradiating the surface of the flexible self-supporting ZnO ultraviolet detector prepared in the embodiment by using an ultraviolet LED with the central wavelength of 365nm, and testing again under the same voltage parameters to obtain an I-V characteristic diagram of the device in a light state.
As shown in fig. 4, it can be seen that the flexible self-supporting ZnO ultraviolet detector prepared in this embodiment has relatively low dark current in a flat state, and the light-dark suppression ratio can reach three orders of magnitude.
2) The flexible self-supporting ZnO ultraviolet detector prepared in this example in a bent state was subjected to a voltage-current (I-V) characteristic curve test in a dark state and under 365nm illumination, and the test procedure was the same as the above test except that the flexible self-supporting ZnO ultraviolet detector was in a bent state at this time.
As shown in fig. 5, it can be seen that the flexible self-supporting ZnO ultraviolet detector prepared in this embodiment also has relatively low dark current in the curved state, and the light-dark suppression ratio can reach three orders of magnitude.
As shown in fig. 6, which is a comparison graph of voltage-current (I-V) characteristic curves of the flexible self-supporting ZnO ultraviolet detector of this embodiment under a flat state and a bent state, under a dark state and under 365nm illumination, it can be seen from the graph that the flexible self-supporting ZnO ultraviolet detector of this embodiment has a potential for manufacturing a flexible device.
The flexible self-supporting ZnO ultraviolet detector adopts the quadruped ZnO nano-structure layer, has a special quadruped structure, takes four nanowires as a unit, each structure unit is tightly connected, the structure is relatively firm, the quadruped ZnO nano-structure layer can be separated from a substrate to independently exist when the thickness is large enough, and the quadruped ZnO nano-structure layer can be stacked into a flocculent self-supporting structure, so that more possibilities are provided for the selection of the substrate of the flexible ultraviolet detector, and the problem that the substrate in the existing ZnO micro-nano structure flexible ultraviolet detector cannot resist high temperature is effectively solved; the four-footed ZnO nanostructure layer has high crystallization quality, excellent performance, high light-dark inhibition ratio and high response speed, can be transferred to a flexible substrate, and can simply and efficiently obtain a flexible ultraviolet detector with high response speed. The preparation method of the flexible self-supporting ZnO ultraviolet detector is simple and efficient, the preparation process of the four-footed ZnO nano-structure layer is controllable and can be designed, and the thickness of the four-footed ZnO nano-structure layer can be designed.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A flexible self-supporting ZnO ultraviolet detector, comprising:
the flexible ZnO nano-structure comprises a quadruped ZnO nano-structure layer, two electrodes arranged on the surface of the quadruped ZnO nano-structure layer and a flexible substrate;
the quadruped ZnO nanostructure layer independently exists to realize self-supporting and is arranged on the flexible substrate through transfer.
2. The flexible self-supporting ZnO ultraviolet detector as claimed in claim 1, wherein the thickness of the quadruped ZnO nanostructure layer is 50-1000 μm; wherein the diameter of each four-foot of the four-foot ZnO nano structure is 50-100 nm, and the length of each four-foot is 2-5 mu m.
3. The flexible self-supporting ZnO ultraviolet detector according to claim 1, characterized In that the two electrodes are independently designed and independently selected from any one of In electrode, Au electrode, Ag electrode or Al electrode, and the thickness of the electrodes is 30-50 nm.
4. The flexible self-supporting ZnO ultraviolet detector as claimed in claim 3, wherein the two electrodes are both circular electrodes with a diameter of 1-2 mm; the distance between the two electrodes is less than or equal to 1 mm.
5. The flexible self-supporting ZnO ultraviolet detector according to claim 1, characterized in that the flexible substrate is a polyethylene terephthalate substrate or a woven fabric substrate.
6. A method for preparing the flexible self-supporting ZnO ultraviolet detector of any one of claims 1 to 5, which is characterized by comprising the following steps:
s1: preparing the quadruped ZnO nanostructure layer;
s2: fixing the two electrodes on the quadruped ZnO nanostructure layer in a bonding mode;
s3: and transferring the quadruped ZnO nano-structure layer bonded with the two electrodes onto the flexible substrate, compacting and fixing, and paving parchment paper before compacting to prevent the quadruped ZnO nano-structure layer from being damaged and stained in the compacting process, thereby obtaining the flexible self-supporting ZnO ultraviolet detector.
7. The method for preparing a flexible self-supporting ZnO ultraviolet detector as claimed in claim 6, wherein the method for preparing the four-footed ZnO nanostructure layer in the step S1 is any one of a flame transport method, a chemical vapor deposition method and a hydrothermal method.
8. The method for preparing a flexible self-supporting ZnO ultraviolet detector according to claim 7, wherein the step S1 is to prepare the quadruped ZnO nanostructure layer by chemical vapor deposition, and the preparation steps are as follows:
s10: grinding and uniformly mixing ZnO powder and graphite powder according to the mass ratio of 1:1, and then placing the mixture in chemical vapor deposition equipment to be used as a growth source;
s11: heating the chemical vapor deposition equipment under the protection of inert gas, wherein the heating control parameters are as follows: (50 +/-1) min is increased from room temperature to 1000 ℃, and (30 +/-1) min is increased from 1000 ℃ to 1130-1150 ℃; when the temperature rises to 1000 ℃, introducing oxygen, and controlling the flow of the oxygen to be 15-20 sccm;
s12: preserving the heat at 1130-1150 deg.c for 60 +/-1 min for growing and depositing four-footed ZnO nanometer structure;
s13: and after the deposition is finished, cooling to room temperature, and directly separating and taking out the ZnO nano-structure layer with tweezers to obtain the quadruped ZnO nano-structure layer.
9. The method for preparing the flexible self-supporting ZnO ultraviolet detector as claimed in claim 8, wherein the inert gas is argon or nitrogen.
10. The method for preparing the flexible self-supporting ZnO ultraviolet detector as claimed in claim 9, wherein the inert gas is argon, and the flow rate of the argon is 90-110 sccm.
CN202010039582.XA 2020-01-15 2020-01-15 Flexible self-supporting ZnO ultraviolet detector and preparation method thereof Active CN111244201B (en)

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