CN103915524A - Self-driven ZnO-based ultraviolet detector and manufacturing method thereof - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000011521 glass Substances 0.000 claims abstract description 27
- 238000003491 array Methods 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- 239000000565 sealant Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000005477 sputtering target Methods 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 208000002925 dental caries Diseases 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000026267 regulation of growth Effects 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000000825 ultraviolet detection Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012742 biochemical analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
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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
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
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- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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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
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1836—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
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Abstract
The invention discloses a self-driven ZnO-based ultraviolet detector. The self-driven ZnO-based ultraviolet detector is sequentially provided with a transparent conductive substrate, a ZnO seed crystal layer, a ZnO nanometer array, an electrolyte layer, an NiS nanometer needle array conductive layer and glass from bottom to top. A manufacturing method of the self-driven ZnO-based ultraviolet detector comprises the steps that the ZnO seed crystal layer is grown on the transparent conductive substrate by the adoption of magnetron sputtering, and then the ZnO nanometer array is grown on the ZnO seed crystal layer through the hydrothermal method; the NiS nanometer needle array conductive layer is grown on the glass through the hydrothermal method; the ZnO nanometer array is covered with the NiS nanometer needle array conductive layer and a cavity which is 20-60 micrometers is formed between the ZnO nanometer array and the NiS nanometer needle array conductive layer; finally, electrolytes are injected into the cavity, the cavity is sealed, and then the self-driven ZnO-based ultraviolet detector is manufactured. Compared with a traditional ultraviolet detector, the self-driven ZnO-based ultraviolet detector has the advantages that bias voltage does not need to be added, the response speed is high, the response sensitivity is high and the structure is simple. In addition, the manufacturing cost is low, large area and large arrays are easy to realize, and the self-driven ZnO-based ultraviolet detector has important application value in military, civil and certain specific fields.
Description
Technical field
The invention belongs to technical field of semiconductor device, refer to especially a kind of self-driven zno-based ultraviolet band detector and preparation method thereof.
Background technology
Ultraviolet detection technology is the another novel Detection Techniques that grow up after infrared and Laser Detection Technique, has a wide range of applications at aspects such as military and civilians.Militarily, missile warning, guidance, ultraviolet communication, biochemical analysis etc.; On civilian, as the analysis of naked light detection, biological medicine, ozone monitoring, offshore oil prison, solar illumination monitoring, public security scouting etc.At present, the U.S. oneself have the solar ultraviolet index wrist-watch that utilizes GaN base ultraviolet detector to prepare of commercial sale.But, also little about the report of self-driven ultraviolet detector.
Semiconductor material with wide forbidden band take ZnO as representative has broad application prospects and receives much concern aspect ultraviolet detector, develops very rapid.ZnO is a kind of environmentally friendly semiconductor material with wide forbidden band, and under room temperature, energy gap is 3.37 eV, has that preparation method is various, high temperature resistant, preparation cost is low, radioresistance and an advantage such as band gap is adjustable.Than traditional film ultraviolet detector, self-driven zno-based ultraviolet detector has more without the advantage such as applying bias, fast response time, response sensitivity be high, simple in structure.And light-sensitive material ZnO nano array can be realized the ultraviolet detection of different-waveband by means such as doping, have and be easy to realize large area, large array, the feature that light-sensitive material is controlled.
Summary of the invention
The object of this invention is to provide that a kind of preparation cost is low, the simple self-driven zno-based ultraviolet detector of technique and preparation method thereof.
Self-driven zno-based ultraviolet detector of the present invention, has electrically conducting transparent substrate, ZnO inculating crystal layer, ZnO nano array, dielectric substrate, NiS nano needle arrays conductive layer and glass from bottom to top successively.
Conventionally, the thickness of ZnO inculating crystal layer is 30～100 nanometers, and the thickness of ZnO nano array is 1 ~ 3 micron; The thickness of NiS nano needle arrays conductive layer is 3～7 microns; In 20～60 microns of cavitys that dielectric substrate forms between ZnO nano array and NiS nano needle arrays conductive layer.
Above-mentioned electrolyte can be deionized water.Described electrically conducting transparent substrate can be FTO glass, AZO glass or ito glass.
The preparation method of self-driven zno-based ultraviolet detector, comprises the following steps:
1) the electrically conducting transparent substrate through clean is put into magnetron sputtering apparatus, take ZnO ceramic target as sputtering target material, 200～500 ℃ of temperature, under 1～5 Pa pressure, carry out Grown by Magnetron Sputtering ZnO inculating crystal layer; Then put into hydrothermal reaction kettle, take zinc nitrate and hexamethylenetetramine as source, the mol ratio of zinc nitrate and hexamethylenetetramine is 1:1, at 80～120 ℃ of insulation 4～10 h, the ZnO nano array of growing on ZnO inculating crystal layer;
2) glass through clean is vertically put into water heating kettle, take nickelous sulfate, thiocarbamide and ammoniacal liquor as source, the mol ratio 1:1:2 of nickelous sulfate, thiocarbamide and ammoniacal liquor is incubated 5～20 h at 100～200 ℃, at growth NiS nano needle arrays conductive layer on glass;
3) by step 2) growth the glass that has NiS nano needle arrays conductive layer cover step 1) ZnO nano array on, make between ZnO nano array and NiS nano needle arrays 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 NiS nano needle arrays conductive layer, with a remaining side of sealant sealing, obtain self-driven zno-based ultraviolet detector again.
Operation principle: ultraviolet light is from the one side incident of electrically conducting transparent substrate back, because the Fermi level of N-shaped semiconductor ZnO nano array is higher than electrolytical Fermi level, therefore electronics will be from ZnO nano array one effluent to an electrolytical side, thereby make band curvature, form carrier depletion layer in ZnO nano array and electrolytical interface and formed internal electric field, form the separation that internal electric field is conducive to light induced electron hole, therefore do not need applied voltage to realize self-driven.
Beneficial effect of the present invention is:
1) the inventive method is simple, is easy to realize large area, large array;
2) high without applying bias, fast response time, response sensitivity;
3), by ZnO nano-wire is adulterated, can realize the ultraviolet detection of different-waveband.
Accompanying drawing explanation
Fig. 1 is self-driven zno-based UV detector structure schematic diagram of the present invention.
In figure: 1 is that electrically conducting transparent substrate, 2 is that ZnO inculating crystal layer, 3 is that ZnO nano array, 4 is that dielectric substrate, 5 is that NiS nano needle arrays conductive layer, 6 is glass.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing.
With reference to Fig. 1, self-driven zno-based ultraviolet detector of the present invention, has electrically conducting transparent substrate 1, ZnO inculating crystal layer 2, ZnO nano array 3, dielectric substrate 4, NiS nano needle arrays conductive layer 5 and glass 6 from bottom to top successively.
Embodiment 1
1) the FTO glass through clean is put into magnetron sputtering apparatus, 300 ℃ of temperature, growth regulation chamber pressure is 2 Pa, sputtering power 100 W, sputtering target material is ZnO ceramic target, growth thickness is the ZnO inculating crystal layer of 50 nanometers, then take zinc nitrate and hexamethylenetetramine as source, the mol ratio of zinc nitrate and hexamethylenetetramine is 1:1,95 ℃ of insulation 6 h in hydrothermal reaction kettle, and on ZnO inculating crystal layer, growth length is the ZnO nano array of 2 microns.
2) glass substrate through clean is vertically put into water heating kettle, take nickelous sulfate, thiocarbamide and ammoniacal liquor as source, the mol ratio 1:1:2 of nickelous sulfate, thiocarbamide and ammoniacal liquor, is incubated 20 h at 150 ℃, and growth length is the NiS nanoneedle conductive layer of 7 microns.
3) by step 2) growth the glass that has NiS nano needle arrays conductive layer cover step 1) ZnO nano array on, make between ZnO nano array and NiS nano needle arrays conductive layer at a distance of 20 microns, first with sealant by three side seals, then deionized water is injected in the cavity between ZnO nano array and NiS nano needle arrays conductive layer, with a remaining side of sealant sealing, obtain self-driven zno-based ultraviolet detector again.
The self-driven zno-based ultraviolet detector response speed that this example makes is 0.5s.
Embodiment 2
1) ito glass through clean is put into magnetron sputtering apparatus, 200 ℃ of temperature, growth regulation chamber pressure is 1 Pa, sputtering power 100 W, sputtering target material is ZnO ceramic target, growth thickness is the ZnO inculating crystal layer of 30 nanometers, then take zinc nitrate and hexamethylenetetramine as source, the mol ratio of zinc nitrate and hexamethylenetetramine is 1:1,80 ℃ of insulation 4 h in hydrothermal reaction kettle, and on ZnO inculating crystal layer 2, growth length is the ZnO nano array of 1 micron.
2) glass substrate through clean is vertically put into water heating kettle, take nickelous sulfate, thiocarbamide and ammoniacal liquor as source, the mol ratio 1:1:2 of nickelous sulfate, thiocarbamide and ammoniacal liquor, is incubated 10 h at 100 ℃, and growth length is the NiS nanoneedle conductive layer of 5 microns.
3) by step 2) growth the glass that has NiS nano needle arrays conductive layer cover step 1) ZnO nano array on, make between ZnO nano array and NiS nano needle arrays conductive layer at a distance of 50 microns, first with sealant by three side seals, then deionized water is injected in the cavity between ZnO nano array and NiS nano needle arrays conductive layer, with a remaining side of sealant sealing, obtain self-driven zno-based ultraviolet detector again.
The self-driven zno-based ultraviolet detector response speed that this example makes is 0.7s.
Embodiment 3
1) the AZO glass through clean is put into magnetron sputtering apparatus, 500 ℃ of temperature, growth regulation chamber pressure is 5 Pa, sputtering power 200 W, sputtering target material is ZnO ceramic target, growth thickness is the ZnO inculating crystal layer of 100 nanometers, then take zinc nitrate and hexamethylenetetramine as source, the mol ratio of zinc nitrate and hexamethylenetetramine is 1:1,120 ℃ of insulation 10 h in hydrothermal reaction kettle, and on ZnO inculating crystal layer, growth length is the ZnO nano array of 3 microns.
2) glass substrate through clean is vertically put into water heating kettle, take nickelous sulfate, thiocarbamide and ammoniacal liquor as source, the mol ratio 1:1:2 of nickelous sulfate, thiocarbamide and ammoniacal liquor, is incubated 5 h at 200 ℃, and growth length is the NiS nanoneedle conductive layer of 3 microns.
3) by step 2) growth the glass that has NiS nano needle arrays conductive layer cover step 1) ZnO nano array on, make between ZnO nano array and NiS nano needle arrays 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 NiS nano needle arrays conductive layer, with a remaining side of sealant sealing, obtain self-driven zno-based ultraviolet detector again.
The self-driven zno-based ultraviolet detector response speed that this example makes is 0.9s.
Claims (5)
1. a self-driven zno-based ultraviolet detector, is characterized in that: have successively electrically conducting transparent substrate (1), ZnO inculating crystal layer (2), ZnO nano array (3), dielectric substrate (4), NiS nano needle arrays conductive layer (5) and glass (6) from bottom to top.
2. self-driven zno-based ultraviolet detector according to claim 1, is characterized in that: the thickness of ZnO inculating crystal layer (2) is 30～100 nanometers, the thickness of ZnO nano array (3) is 1 ~ 3 micron; The thickness of NiS nano needle arrays conductive layer is 3～7 microns; In 20～60 microns of cavitys that dielectric substrate (4) forms between ZnO nano array (3) and NiS nano needle arrays conductive layer (5).
3. self-driven zno-based ultraviolet detector according to claim 1, is characterized in that: described dielectric substrate is deionized water.
4. self-driven zno-based ultraviolet detector according to claim 1, is characterized in that: described electrically conducting transparent substrate (1) is FTO glass, AZO glass or ito glass.
5. the method for preparation self-driven zno-based ultraviolet detector claimed in claim 1, comprises the following steps:
1) the electrically conducting transparent substrate (1) through clean is put into magnetron sputtering apparatus, take ZnO ceramic target as sputtering target material, 200～500 ℃ of temperature, under 1～5 Pa pressure, carry out Grown by Magnetron Sputtering ZnO inculating crystal layer (2); Then put into hydrothermal reaction kettle, take zinc nitrate and hexamethylenetetramine as source, the mol ratio of zinc nitrate and hexamethylenetetramine is 1:1, at 80～120 ℃ of insulation 4～10 h, the ZnO nano array (3) of growing on ZnO inculating crystal layer;
2) glass through clean (6) is vertically put into water heating kettle, take nickelous sulfate, thiocarbamide and ammoniacal liquor as source, the mol ratio of nickelous sulfate, thiocarbamide and ammoniacal liquor is 1:1:2, is incubated 5～20 h at 100～200 ℃, at growth NiS nano needle arrays conductive layer on glass (5);
3) by step 2) growth have the glass of NiS nano needle arrays conductive layer to cover step 1) ZnO nano array on, make between ZnO nano array (3) and NiS nano needle arrays 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 NiS nano needle arrays conductive layer (5), with a remaining side of sealant sealing, obtain self-driven zno-based ultraviolet detector again.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465112A (en) * | 2014-12-11 | 2015-03-25 | 浙江大学 | Self-driven ZnO-based ultraviolet detector based on flexible substrates and preparation method thereof |
| CN105390615A (en) * | 2015-11-30 | 2016-03-09 | 中国科学技术大学 | UV light sensor |
| US9806125B2 (en) | 2015-07-28 | 2017-10-31 | Carrier Corporation | Compositionally graded photodetectors |
| US9865766B2 (en) | 2015-07-28 | 2018-01-09 | Carrier Corporation | Ultraviolet photodetectors and methods of making ultraviolet photodetectors |
| US9928727B2 (en) | 2015-07-28 | 2018-03-27 | Carrier Corporation | Flame detectors |
| CN108258121A (en) * | 2018-01-15 | 2018-07-06 | 苏州大学 | Organo-mineral complexing drives photodetector and preparation method thereof certainly |
| US10126165B2 (en) | 2015-07-28 | 2018-11-13 | Carrier Corporation | Radiation sensors |
| CN113804292A (en) * | 2021-07-13 | 2021-12-17 | 重庆师范大学 | Photoelectrochemical self-powered solar blind deep ultraviolet photoelectric detector and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465112A (en) * | 2014-12-11 | 2015-03-25 | 浙江大学 | Self-driven ZnO-based ultraviolet detector based on flexible substrates and preparation method thereof |
| US9806125B2 (en) | 2015-07-28 | 2017-10-31 | Carrier Corporation | Compositionally graded photodetectors |
| US9865766B2 (en) | 2015-07-28 | 2018-01-09 | Carrier Corporation | Ultraviolet photodetectors and methods of making ultraviolet photodetectors |
| US9928727B2 (en) | 2015-07-28 | 2018-03-27 | Carrier Corporation | Flame detectors |
| US10126165B2 (en) | 2015-07-28 | 2018-11-13 | Carrier Corporation | Radiation sensors |
| US10718662B2 (en) | 2015-07-28 | 2020-07-21 | Carrier Corporation | Radiation sensors |
| US11029202B2 (en) | 2015-07-28 | 2021-06-08 | Carrier Corporation | Radiation sensors |
| CN105390615A (en) * | 2015-11-30 | 2016-03-09 | 中国科学技术大学 | UV light sensor |
| CN105390615B (en) * | 2015-11-30 | 2018-10-23 | 中国科学技术大学 | A kind of ultraviolet light transducer |
| CN108258121A (en) * | 2018-01-15 | 2018-07-06 | 苏州大学 | Organo-mineral complexing drives photodetector and preparation method thereof certainly |
| CN113804292A (en) * | 2021-07-13 | 2021-12-17 | 重庆师范大学 | Photoelectrochemical self-powered solar blind deep ultraviolet photoelectric detector and preparation method thereof |
| CN113804292B (en) * | 2021-07-13 | 2023-06-09 | 重庆师范大学 | Photoelectrochemistry type self-powered solar blind deep ultraviolet photoelectric detector and preparation method thereof |
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