CN104465112A - Self-driven ZnO-based ultraviolet detector based on flexible substrates and preparation method thereof - Google Patents
Self-driven ZnO-based ultraviolet detector based on flexible substrates and preparation method thereof Download PDFInfo
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- CN104465112A CN104465112A CN201410754808.9A CN201410754808A CN104465112A CN 104465112 A CN104465112 A CN 104465112A CN 201410754808 A CN201410754808 A CN 201410754808A CN 104465112 A CN104465112 A CN 104465112A
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Abstract
The invention discloses a self-driven ZnO-based ultraviolet detector based on flexible substrates. The transparent conductive flexible substrate, a ZnO seed crystal layer, a ZnO nano array, an electrolyte layer, a Pt conductive layer and the flexible substrate are sequentially arranged from bottom to top. A preparation method of the self-driven ZnO-based ultraviolet detector comprises the steps that a laser pulse deposition method is adopted for growing the ZnO seed crystal layer on the transparent conductive flexible substrate, and the ZnO nano array is grown on the ZnO seed crystal layer in a hydrothermal mode; an electron beam evaporation method is adopted for evaporating the Pt conductive layer on the flexible substrate; the ZnO nano array is covered with the Pt conductive layer, and a cavity with the size ranging from 20 micrometers to 60 micrometers is formed between the ZnO nano array and the Pt conductive layer; finally, the cavity is filled with electrolyte, and the self-driven ZnO-based ultraviolet detector based on the flexible substrates is obtained in a sealed mode. Compared with a traditional ultraviolet detector, the self-driven ZnO-based ultraviolet detector has the advantages that no additional bias voltage needs to be added, the response speed is high, sensitivity is high, the structure is simple, and the self-driven ZnO-based ultraviolet detector can be carried and folded. In addition, the preparation cost is low, large-area production is easy to achieve, and the self-driven ZnO-based ultraviolet detector has the wide application prospects in military, civilian use, small portable electric appliances and some special occasions like a field.
Description
Technical field
The invention belongs to technical field of semiconductor device, refer to especially a kind of flexibility and self-driven zno-based ultraviolet band detector and preparation method thereof.
Background technology
The research of ultraviolet detection has important practical significance.The product that ultra-violet radiation normally burns, the wake flame of rocket and jet, the burning of hydrocarbon can produce stronger ultra-violet radiation.In living environment, the sun is the most powerful UV source, but after Gaseous attenuation, the spectrum blind area of solar radiation is there is in ground and near-earth air, the ultraviolet being in air ultraviolet window spectrum district presents uniform background because of atmospheric scattering, if effectively utilize this spectrum blind area just can detect the UV source of non-solar, it is monitored, have a wide range of applications in military and civilian etc.Militarily, missile warning, guidance, ultraviolet communication, biochemical analysis etc.; On civilian, as the analysis, ozone monitoring, offshore oil prison, solar illumination monitoring, public security scouting etc. of naked light detection, biological medicine.Most widely used is ultraviolet vacuum diode, ultravioplet photomultiplier etc. at present, but the report about self-driven ultraviolet detector is also little, and especially the self-driven ultraviolet detector of flexible substrate photochemical cell structure is not also reported.
ZnO is a kind of semiconductor material with wide forbidden band, and under room temperature, energy gap is 3.37 eV, is subject to paying close attention to more and more widely in ultraviolet detection.ZnO has that preparation method is various, high temperature resistant, epitaxial temperature is low, preparation cost is low, radiation resistance is strong and the advantage such as band gap is adjustable.Compared to traditional film ultraviolet detector, flexible substrate self-driven zno-based ultraviolet detector has more without the need to applying bias, fast response time, response sensitivity is high, structure is simple, can carry, the advantage such as collapsible.
Summary of the invention
The object of this invention is to provide that a kind of preparation cost is low, the simple and self-driven zno-based ultraviolet detector based on flexible substrate of function admirable and preparation method thereof of technique.
Self-driven zno-based ultraviolet detector based on flexible substrate of the present invention, has electrically conducting transparent flexible substrate, ZnO inculating crystal layer, ZnO nano array, dielectric substrate, Pt conductive layer and flexible substrate from bottom to top successively.
Usually, the thickness of ZnO inculating crystal layer is 20 ~ 100 nanometers, and the thickness of ZnO nano array is 1 ~ 4 micron; The thickness of Pt conductive layer is 60 ~ 100 nanometers; In 20 ~ 60 microns of cavitys that dielectric substrate is formed between ZnO nano array and Pt conductive layer.
Above-mentioned electrolyte can be deionized water.Described electrically conducting transparent flexible substrate can be the PET being coated with ITO conducting film.
Based on the preparation method of the self-driven zno-based ultraviolet detector of flexible substrate, comprise the following steps:
1) the electrically conducting transparent flexible substrate through clean is put into pulsed laser deposition equipment, with ZnO ceramic target for target, at 20 ~ 60 DEG C, under 1 ~ 3 Pa condition, growth ZnO inculating crystal layer; Then put into hydrothermal reaction kettle, with two water zinc acetates and hexamethylenetetramine for source, the mol ratio of two water zinc acetates and hexamethylenetetramine is 1:1, at 80 ~ 95 DEG C of insulation 4 ~ 10 h, ZnO inculating crystal layer grows ZnO nano array;
2) flexible substrate through clean being put into electron beam evaporation equipment, take Pt metal as evaporation source, and controlling the speed of growth is 0.7 ~ 1.1 dust meter per second, grows Pt conductive layer on flexible substrates;
3) by step 2) growth have the flexible substrate of Pt conductive layer to cover in the ZnO nano array of step 1), make between ZnO nano array and Pt conductive layer at a distance of 20 ~ 60 microns, first with sealant by three side seals, then electrolyte is injected in the cavity between ZnO nano array and Pt conductive layer, again with the side that sealant sealing is remaining, obtain the self-driven zno-based ultraviolet detector based on flexible substrate.
Operation principle: ultraviolet light has the side, the electrically conducting transparent flexible substrate back side of ZnO nano array incident from long, after electrolyte contacts with ZnO nano array, because the Fermi level of N-shaped ZnO nano array is higher than electrolytical Fermi level, therefore electronics will flow to electrolytical side from ZnO nano array side, cause to be with and be bent upwards towards this side of electrolyte, nano-array and electrolytical interface define carrier depletion layer and namely define internal electric field.Under UV-irradiation, electron hole pair is excited, electron hole is quick separating under internal electric field effect, electronics arrives electrode through external circuit after the motion of zinc oxide side arrives work electrode, hole is to electrolyte one lateral movement, and under the catalysis of Pt, a series of redox reaction capable of circulation occurs for electronics and hole and electrolyte, form loop, therefore do not need applied voltage to realize self-driven.
Beneficial effect of the present invention is:
1) the inventive method is simple, and preparation cost is low and be easy to realize large area and produce;
2) high without the need to applying bias, fast response time, response sensitivity;
3) by adulterating to ZnO nano-wire, can realize the ultraviolet detection of different-waveband;
4) whole device can free bend, and device lightweight, can make wearable product, easy to carry, can use under the occasion having special requirement.
Accompanying drawing explanation
Fig. 1 is the structural representation of the self-driven zno-based ultraviolet detector based on flexible substrate of the present invention.
In figure: 1 be electrically conducting transparent flexible substrate, 2 be ZnO inculating crystal layer, 3 be ZnO nano array, 4 be dielectric substrate, 5 be Pt conductive layer, 6 for flexible substrate.
Embodiment
The present invention is described in detail below in conjunction with accompanying drawing.
With reference to Fig. 1, the self-driven zno-based ultraviolet detector based on flexible substrate of the present invention, has electrically conducting transparent flexible substrate 1, ZnO inculating crystal layer 2, ZnO nano array 3, dielectric substrate 4, Pt conductive layer 5 and flexible substrate 6 from bottom to top successively.
Embodiment 1
1) the PET substrate being coated with ITO conducting film through clean is put into pulsed laser deposition equipment, with ZnO ceramic target for target, growth regulation temperature 60 DEG C, pressure is 1 Pa, and growth thickness is the ZnO inculating crystal layer of 50 nanometers; Then put into hydrothermal reaction kettle, with two water zinc acetates and hexamethylenetetramine for source, the mol ratio of two water zinc acetates and hexamethylenetetramine is 1:1, and at 90 DEG C of insulation 4 h, on ZnO inculating crystal layer, growth length is the ZnO nano array of 2 microns;
2) the PET flexible substrate through clean being put into electron beam evaporation equipment, take Pt metal as evaporation source, and controlling the speed of growth is 0.7 ~ 1.1 dust meter per second, and PET grows Pt conductive layer, and thickness is 100 nm;
3) by step 2) growth have the PET of Pt conductive layer to cover in the ZnO nano array of step 1), make between ZnO nano array and Pt conductive layer at a distance of 20 microns, first with sealant by three side seals, then deionized water is injected in the cavity formed between ZnO nano array and Pt conductive layer, again with the side that sealant sealing is remaining, obtain the self-driven zno-based ultraviolet detector based on flexible substrate.
The self-driven ultraviolet detector response speed based on flexible substrate that this example obtains is 0.13 s.
Embodiment 2
1) the PET substrate being coated with ITO conducting film through clean is put into pulsed laser deposition equipment, with ZnO ceramic target for target, growth regulation temperature 45 DEG C, pressure is 2 Pa, and growth thickness is the ZnO inculating crystal layer of 20 nanometers; Then put into hydrothermal reaction kettle, with two water zinc acetates and hexamethylenetetramine for source, the mol ratio of two water zinc acetates and hexamethylenetetramine is 1:1, and at 95 DEG C of insulation 7 h, on ZnO inculating crystal layer, growth length is the ZnO nano array of 4 microns;
2) the PET flexible substrate through clean being put into electron beam evaporation equipment, take Pt metal as evaporation source, and controlling the speed of growth is 0.7 ~ 1.1 dust meter per second, and PET grows Pt conductive layer, and thickness is 60 nm;
3) by step 2) growth have the PET of Pt conductive layer to cover in the ZnO nano array of step 1), make between ZnO nano array and Pt conductive layer at a distance of 40 microns, first with sealant by three side seals, then deionized water is injected in the cavity between ZnO nano array and Pt conductive layer, again with the side that sealant sealing is remaining, obtain the self-driven zno-based ultraviolet detector based on flexible substrate.
The self-driven ultraviolet detector response speed based on flexible substrate that this example obtains is 0.17 s.
Embodiment 3
1) the PET substrate being coated with ITO conducting film through clean is put into pulsed laser deposition equipment, with ZnO ceramic target for target, growth regulation temperature 20 DEG C, pressure is 3 Pa, and growth thickness is the ZnO inculating crystal layer of 100 nanometers; Then put into hydrothermal reaction kettle, with two water zinc acetates and hexamethylenetetramine for source, the mol ratio of two water zinc acetates and hexamethylenetetramine is 1:1, and at 80 DEG C of insulation 10 h, on ZnO inculating crystal layer, growth length is the ZnO nano array of 1 micron;
2) the PET flexible substrate through clean being put into electron beam evaporation equipment, take Pt metal as evaporation source, and controlling the speed of growth is 0.7 ~ 1.1 dust meter per second, and PET grows Pt conductive layer, and thickness is 80 nm;
3) by step 2) growth have the PET of Pt conductive layer to cover in the ZnO nano array of step 1), make between ZnO nano array and Pt conductive layer at a distance of 60 microns, first with sealant by three side seals, then deionized water is injected in the cavity between ZnO nano array and Pt conductive layer, again with the side that sealant sealing is remaining, obtain the self-driven zno-based ultraviolet detector based on flexible substrate.
The self-driven ultraviolet detector response speed based on flexible substrate that this example obtains is 0.15 s.
Claims (5)
1., based on a self-driven zno-based ultraviolet detector for flexible substrate, it is characterized in that having electrically conducting transparent flexible substrate (1), ZnO inculating crystal layer (2), ZnO nano array (3), dielectric substrate (4), Pt conductive layer (5) and flexible substrate (6) from bottom to top successively.
2. the self-driven zno-based ultraviolet detector based on flexible substrate according to claim 1, the thickness that it is characterized in that described ZnO inculating crystal layer (2) is 20 ~ 100 nanometers, the thickness of ZnO nano array (3) is 1 ~ 4 micron, and the thickness of Pt conductive layer (5) is 60 ~ 100 nanometers; In 20 ~ 60 microns of cavitys that dielectric substrate (4) is formed between ZnO nano array (3) and Pt conductive layer (5).
3. the self-driven zno-based ultraviolet detector based on flexible substrate according to claim 1, is characterized in that described dielectric substrate is deionized water.
4. the self-driven zno-based ultraviolet detector based on flexible substrate according to claim 1, is characterized in that described electrically conducting transparent flexible substrate (1) is the PET being coated with ITO conducting film.
5. prepare the method for the self-driven zno-based ultraviolet detector based on flexible substrate according to claim 1, it is characterized in that comprising the following steps:
1) the electrically conducting transparent flexible substrate (1) through clean is put into pulsed laser deposition equipment, with ZnO ceramic target for target, at 20 ~ 60 DEG C, under 1 ~ 3 Pa condition, growth ZnO inculating crystal layer (2); Then put into hydrothermal reaction kettle, with two water zinc acetates and hexamethylenetetramine for source, the mol ratio of two water zinc acetates and hexamethylenetetramine is 1:1, at 80 ~ 95 DEG C of insulation 4 ~ 10 h, ZnO inculating crystal layer grows ZnO nano array (3);
2) flexible substrate (6) through clean being put into electron beam evaporation equipment, take Pt metal as evaporation source, and controlling the speed of growth is 0.7 ~ 1.1 dust meter per second, in flexible substrate (6) upper growth Pt conductive layer (5);
3) by step 2) growth have the flexible substrate of Pt conductive layer to cover in the ZnO nano array of step 1), make between ZnO nano array (3) and Pt conductive layer (5) at a distance of 20 ~ 60 microns, first with sealant by three side seals, then electrolyte (4) is injected in the cavity between ZnO nano array (3) and Pt conductive layer (5), again with the side that sealant sealing is remaining, obtain the self-driven zno-based ultraviolet detector based on flexible substrate.
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| CN105390615A (en) * | 2015-11-30 | 2016-03-09 | 中国科学技术大学 | UV light sensor |
| CN106057956A (en) * | 2016-06-27 | 2016-10-26 | 浙江大学 | Ionic-liquid-gel-electrolyte-based quasi-solid flexible self-powered ZnO-based ultraviolet detector and preparation method thereof |
| CN107046084A (en) * | 2017-04-06 | 2017-08-15 | 大连理工大学 | A kind of preparation method of the ZnO ultraviolet detectors based on flexible polymer substrate |
| CN108535337A (en) * | 2018-05-30 | 2018-09-14 | 杨丽娜 | Flexible gas sensor and preparation method thereof based on tin oxide/gallium oxide hetero-junctions nano-array |
| CN109003889A (en) * | 2018-07-30 | 2018-12-14 | 合肥工业大学 | The preparation method of II-VI group semiconductive thin film in a kind of flexible substrates |
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| CN107046084A (en) * | 2017-04-06 | 2017-08-15 | 大连理工大学 | A kind of preparation method of the ZnO ultraviolet detectors based on flexible polymer substrate |
| CN108535337A (en) * | 2018-05-30 | 2018-09-14 | 杨丽娜 | Flexible gas sensor and preparation method thereof based on tin oxide/gallium oxide hetero-junctions nano-array |
| CN109003889A (en) * | 2018-07-30 | 2018-12-14 | 合肥工业大学 | The preparation method of II-VI group semiconductive thin film in a kind of flexible substrates |
| CN109003889B (en) * | 2018-07-30 | 2021-09-17 | 合肥工业大学 | Preparation method of II-VI semiconductor film on flexible substrate |
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