CN103400900B - ZnO quantum dot base deep UV sensor and preparation method - Google Patents
ZnO quantum dot base deep UV sensor and preparation method Download PDFInfo
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- CN103400900B CN103400900B CN201310346886.0A CN201310346886A CN103400900B CN 103400900 B CN103400900 B CN 103400900B CN 201310346886 A CN201310346886 A CN 201310346886A CN 103400900 B CN103400900 B CN 103400900B
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000005622 photoelectricity Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000004888 barrier function Effects 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 230000006641 stabilisation Effects 0.000 abstract description 4
- 238000011105 stabilization Methods 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 59
- 239000011787 zinc oxide Substances 0.000 description 29
- 239000011701 zinc Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 nanometer rods Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention relates to ZnO quantum dot base deep UV sensor and preparation method.The present invention using ultra-fine ZnO quantum dot network structure as photoelectric respone active layer, be the preparation process for arriving ZnO quantum dot base deep UV sensor again by the preparation of ZnO quantum dot.The present invention solve over existing for the process of oxygen adsorption and desorption that is occurred based on ZnO surfaces of switch of photoelectric current a big defect of effective Schottky barrier difficulty is designed slowly and in device.The present invention devises a new deep ultraviolet detector part based on ZnO quantum dot using easy, low cost self-assembly process, it shows spectral selection high, the photoswitch behavior of stabilization, photocurrent response degree high and quick response speed, with significant, quick and stabilization photoelectric current switching characteristic：Photoelectric current on-off ratio is more than 103, photoelectric current rises and die-away time is both less than 1s, improves the response speed of UV detectors.
Description
Technical field
The invention belongs to field of functional materials, more particularly to ZnO quantum dot base deep UV sensor and preparation method.
Background technology
Ultraviolet (UV) senser element has extensive demand in industry and scientific domain, such as in thermal-flame, guided missile flame plumage
Monitoring, ambient light detection and the field such as photoswitch and optic communication suffer from direct application prospect.Zinc oxide (ZnO) conduct
One typical wide bandgap semiconductor (Eg~3.4eV), it has preferable exciton bind energy (Eb~60meV), it is that exploitation UV is visited
Survey one of ideal material of device.In recent years, because monodimension nanometer material has natural electron propagation ducts and larger ratio table
The 1-dimention nano building blocks such as area, ZnO nano-wire, nanometer rods, nanobelt are widely used in designing UV detectors.However,
In the 1-dimention nano UV sensitive detection parts of Ohmic contact, the time of photoelectric respone generally needs several seconds to a few minutes even several percentages
Clock, because the process of oxygen adsorption and desorption of the switch of photoelectric current based on the generation of ZnO surfaces is slowly.Table is studied recently
Bright, the Schottky barrier formed between ZnO nano-structure and electrode can effectively improve the speed of photoelectric respone, especially extensive
The rate of decay of photoelectric current during multiple.But, it is still an arduousness that an effective Schottky barrier is designed in the devices
Task.It is well known that there is junction barrier between particle in continuous membrana granulosa, they are equivalent to isotropic Schottky gesture
Base hampers the transmission of electronics, and its barrier height is quickly sensitive to photoproduction carrier concentration, therefore such junction barrier master
Lead conductance and its photoelectric respone of membrana granulosa.
The content of the invention
It is an object of the invention to overcome drawbacks described above, ZnO quantum dot base deep UV sensor preparation method is developed.
The technical scheme is that：
ZnO quantum dot base deep UV sensor, it is mainly characterized by using ultra-fine ZnO quantum dot network structure
As the active layer of photoelectric respone.
Another technical scheme of the invention is：
ZnO quantum dot base deep UV sensor preparation method, its major technique step is：
The preparation of ZnO quantum dot：
(1) by Zn (CH3COO)2·2H2O powder is added in absolute dry ethanol solution, and the solution is continuous at 80 DEG C
The solution is cooled to 0 DEG C by stirring to fully dissolving with ice bath；
(2) by LiOHH2O powder ultrasonics are dissolved in absolute dry ethanol solution, prepare uniform LiOH solution；
(3) the LiOH solution for obtaining step (2) dropwise lentamente adds the Zn (CH that step (1) is obtained3COO)2Ethanol
In solution, reacted at 0 DEG C, be aided with magnetic stirring and N2The protection of air-flow；
(4) ZnO quantum dot solution is obtained, being placed in less than 0 DEG C in absolute dry ethanol preserves；The preparation of sensor：
(5) Au interdigital electrodes are put into the ethanol solution of the ZnO quantum dot that step (4) is obtained；
(6) and then to normal heptane is added dropwise in the solution, ZnO quantum dot gradually overflows and is deposited on Au interdigital electrodes
On；
(7) by after fully deposition, the Au interdigital electrodes that will deposit has ZnO quantum dot are proposed, and in N2Lower cool drying.
The ZnO quantum dot base Ultraviolet sensor of present invention design has the advantage that：1. process units is simple, techniqueflow
Simply, it is with low cost, can mass and industrialization；2. there is significant, quick and stabilization photoelectric current switching characteristic：Photoelectric current
On-off ratio is more than 103, photoelectric current rises and die-away time is both less than 1s；3. selected with light wave higher and more meaning
Property, only the deep UV to wavelength less than 340nm has significant response.
The present invention devises one and is based on the new dark purple of ZnO quantum dot using easy, low cost self-assembly process
External detector part, it shows spectral selection high, the photoswitch behavior of stabilization, photocurrent response degree high and quickly rings
Speed is answered, the response speed of UV detectors is improve.
Brief description of the drawings
Fig. 1 --- the building process schematic diagram of ZnO quantum dot base Ultraviolet sensor self assembly in the present invention.
Fig. 2 --- the ZnO quantum dot base Ultraviolet sensor of present invention design is in the ultraviolet of ambient white light, 355nm and 325nm
I-V curve schematic diagram under light irradiation；Wherein, the I-V curve funerary objects part of linear symmetric is presented Ohmic contact in Fig. 2 (a), and
And photoelectric current only just has significant enhancing under the dark purple external exposure of 325nm, illustrate that device is only more sensitive to DUV, i.e.,
With higher, more meaning light wave selectivity；Fig. 2 (b) shows the I-V curve in logarithmic coordinates system, apparent earth's surface
The on-off ratio of Mingguang City's electric current is higher than 103, and be hardly dependent on and bias (0.1~5V).
Fig. 3 --- the ZnO quantum dot base Ultraviolet sensor of present invention design is in 325nm ultraviolet irradiations (22.9mW/cm2) and
Time-resolved photoelectric respone curve synoptic diagram under 5V biass；Wherein, Fig. 3 (a) shows device with stable, quick and notable
Photoelectric current switching behaviour；The rising of Fig. 3 (b) display photoelectric currents and attenuation process meet bi-exponential fitting, corresponding time
Index respectively may be about 0.8s and 0.5s.
Specific embodiment
Technical thought of the invention is：
A UV sensitive detection parts are built as construction module, it is desirable to by the use of ZnO quantum dot network using between quantum dot
Junction barrier improves the speed of UV photoelectric respones.Additionally, ZnO quantum dot also has two other advantage as building block：1. extra small
Quantum dot there is strong quantum size effect, its band gap can further reduce the wavelength of response spectrum by greatly broadening,
The spectral selection of detection is improved, and it is because deeper ultraviolet radiation on organisms system has bigger harm therefore deep
Degree ultraviolet detection is more meaningful；2. quantum dot has very big absorption coefficient and specific surface area high, can further carry
The efficiency of light absorption of device high and photoelectric respone enliven area.
Front is that specific preparation scheme of the invention is divided into two steps：
The preparation method of first step ZnO quantum dot, its preparation process is as follows：
By 2.18g (10mmol) Zn (CH3COO)2·2H2O powder is added in the absolute dry ethanol solution of 100mL, will be molten
Liquid continuously stirs 3 hours to ensure fully dissolving at 80 DEG C.Then, solution is cooled to 0 DEG C with ice bath.Meanwhile, will
0.59g(14mmol)LiOH·H2O powder ultrasonics are dissolved in 100mL definitely dry ethanol, prepare uniform L.OH solution.To match somebody with somebody
The LiOH solution for making dropwise lentamente adds above-mentioned Zn (CH3COO)2Ethanol solution in, reaction carried out at 0 DEG C 2 hours,
And with violent magnetic stirring and N2The protection of air-flow.Finally, the ZnO quantum dot solution of acquisition is water white transparency, using second
Alcohol and hexane alternating centrifugal wash 6 times to remove remaining reagent and impurity group, and washed ZnO quantum dot is dispersed in again
Less than 0 DEG C is placed in absolute ethanol to preserve.
The construction of second step device, its preparation process is as follows：
The cheap of Au interdigital electrodes deposited in ceramic substrate by easy batch printing process and side
Just buy, raceway groove gets over the Au interdigital electrodes of 180nm, and the interdigital electrode is put into the ethanol solution of the ZnO quantum dot for preparing,
Then to normal heptane is added dropwise in solution, under the ultra violet lamp of 254nm, the ZnO quantum dot of bluish-green fluorescence gradually overflows
And be deposited in Au interdigital electrodes, by after the abundant deposition of 10 minutes, with syringe by the water white transparency part of superjacent
Extract, the Au interdigital electrodes that will lentamente deposit has ZnO quantum dot are proposed, and in N2Lower cool drying, that is, obtain ZnO quantum dot
Base deep UV sensor, so that by the use of ultra-fine ZnO quantum dot network structure as the active layer of photoelectric respone.
As can be seen here, preparation method of the invention is unique, and the method under its inspiration should be regarded as this
The sought protection domain of invention, the i.e. protection domain of application claims is not limited to the description of this specific embodiment.
Claims (2)
- The quantum dot-based deep UV sensors of 1.ZnO, it is characterised in that rung as photoelectricity by the use of ultra-fine ZnO quantum dot network structure The active layer answered, the ZnO quantum dot base deep UV sensor is by Au interdigital electrodes and is deposited in the Au interdigital electrodes Ultra-fine ZnO quantum dot network structure composition.
- 2. ZnO quantum dot base deep UV sensor preparation method according to claim 1, its step is：ZnO quantum dot Preparation：(1) by Zn (CH3COO)2·2H2O powder is added in absolute dry ethanol solution, and the solution is continuously stirred at 80 DEG C To fully dissolving, the solution is cooled to 0 DEG C with ice bath；(2) by LiOH.H2O powder ultrasonics are dissolved in absolute dry ethanol solution, prepare uniform LiOH solution；(3) the LiOH solution for obtaining step (2) dropwise lentamente adds the Zn (CH that step (1) is obtained3COO)2Ethanol solution In, reacted at 0 DEG C, it is aided with magnetic stirring and N2The protection of air-flow；(4) ZnO quantum dot solution is obtained, being placed in less than 0 DEG C in absolute dry ethanol preserves；The preparation of sensor：(5) Au interdigital electrodes are put into the ethanol solution of the ZnO quantum dot that step (4) is obtained；(6) and then to normal heptane is added dropwise in the solution, under the ultra violet lamp of 254nm, the ZnO quantum dot of bluish-green fluorescence Gradually overflow and be deposited in Au interdigital electrodes；(7) by after fully deposition, the Au interdigital electrodes that will deposit has ZnO quantum dot are proposed, and in N2Lower cool drying.
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| CN102703061A (en) * | 2012-05-28 | 2012-10-03 | 扬州大学 | Method for performing fluorescent anti-counterfeit by ZnO quantum dots |
| CN202633358U (en) * | 2011-12-22 | 2012-12-26 | 安徽康蓝光电股份有限公司 | Ultraviolet-visible photoelectric detector with quantum dot structure |
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| CN202633358U (en) * | 2011-12-22 | 2012-12-26 | 安徽康蓝光电股份有限公司 | Ultraviolet-visible photoelectric detector with quantum dot structure |
| CN102703061A (en) * | 2012-05-28 | 2012-10-03 | 扬州大学 | Method for performing fluorescent anti-counterfeit by ZnO quantum dots |
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