CN107342364A - A kind of UV photodetector of zinc oxide polyaniline sandwich structure and preparation method thereof - Google Patents
A kind of UV photodetector of zinc oxide polyaniline sandwich structure and preparation method thereof Download PDFInfo
- Publication number
- CN107342364A CN107342364A CN201710369125.5A CN201710369125A CN107342364A CN 107342364 A CN107342364 A CN 107342364A CN 201710369125 A CN201710369125 A CN 201710369125A CN 107342364 A CN107342364 A CN 107342364A
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- Prior art keywords
- polyaniline
- nano
- zinc oxide
- photodetector
- zinc
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to field of inorganic nano material, discloses a kind of UV photodetector of zinc oxide polyaniline sandwich structure and preparation method thereof.The detector is assembled using ITO electro-conductive glass as substrate by one layer of polyaniline nano-line above the one layer of zinc-oxide nano chip arrays and zinc-oxide nano chip arrays on ITO.The preparation method of the UV photodetector comprises the following steps：One layer of zinc-oxide nano chip arrays are first prepared on ITO substrates using electrochemical process, then polyaniline nano-line is prepared by chemical oxidization method, the polyaniline nano-line of gained is coated with zinc-oxide nano chip arrays again, finally products therefrom is assembled, that is, described UV photodetector is made.The nano-scale and pattern of material bring bigger specific surface area, add the site of material and action of ultraviolet light so that the characteristics of UV photodetector has a stable performance, high sensitivity, and the response time is short.
Description
Technical field
The invention belongs to field of inorganic nano material, more particularly to a kind of zinc oxide-polyaniline sandwich structure it is ultraviolet
Photodetector and preparation method thereof.
Background technology
Before UV photodetector has wide application in green illumination, optical communication, environmental monitoring and national defence etc.
Scape, there is high military and civilian to be worth, be one of study hotspot in photodetection field in the world in recent years.Traditional purple
External detector is based on ultravioplet photomultiplier, but its manufacturing process is complex, and volume is big, fragile, and condition of work will
Ask high, seriously limit its extensive use and development.In recent years, growing wide bandgap semiconductor grinding for ultraviolet detector
Study carefully and opened up new field, be possibly realized using semiconductor ultraviolet detection device instead of traditional ultravioplet photomultiplier.
Zinc oxide is a kind of broad stopband direct band-gap semicondictor material, at room temperature energy gap 3.37eV, exciton bind energy
Up to 60eV, and there is good chemical stability and heat endurance, there is huge application in terms of UV photodetector
Potentiality.Zinc oxide nano sheet has the characteristics of specific surface area is big, and electron transfer rate is fast, and this preferably appearance structure is photosensitive
The fields such as device, gas sensitive device and DSSC show excellent performance.
But zinc oxide is susceptible to the corrosion of light, and sun light absorption wavelength narrow scope, only there is sound to ultraviolet light
Should, it is seen that light utilization ratio is low：Meanwhile the recombination rate of nano zine oxide photo-generated carrier is higher, quantum efficiency is relatively low.Therefore,
Zinc oxide semi-conductor is carried out composite modified to accelerate light induced electron-hole to separation, suppress Carrier recombination to improve quantum
Efficiency；Visible light utilization ratio is improved, is had important practical significance.
Polyaniline belongs to p-type semiconductor's conducting polymer, and simple with synthetic method, stability is good, high temperature resistant
And the advantages that anti-oxidant.In addition, the polyaniline of acid doping has very strong absorption in visible ray and infrared region.Experiment shows, will receive
Rice zinc oxide and polyaniline are compound, can form good heterojunction boundary, be advantageous to the separation in light induced electron-hole pair, carry
The quantum efficiency of high composite and the utilization ratio to visible ray.
The content of the invention
For a long time, zinc-oxide nano chip arrays are big and electricity conversion height has attracted vast scientific research with its specific surface area
The sight of worker, but conventional preparation technology is complicated, and gained nanometer sheet pattern is unstable, it is difficult to exist as base material
It is applied in UV photodetector part.For example, Chinese invention 201310064916.9 discloses a kind of zinc oxide/polyaniline
The method of composite photo-catalyst, its used zinc oxide pattern are much smaller than zinc-oxide nano chip arrays of the present invention, influence
Its utilization ratio to ultraviolet light；Patent 201410685786.5 discloses a kind of preparation method of Zinc oxide nano sheet, its
Complex process, it is difficult to utilized extensively.The shortcomings that in order to overcome prior art, is to carry with deficiency, primary and foremost purpose of the invention
For a kind of UV photodetector of zinc oxide-polyaniline sandwich structure.
Another object of the present invention is to provide a kind of ultraviolet photoelectric detection of above-mentioned zinc oxide-polyaniline sandwich structure
The preparation method of device.
The purpose of the present invention is achieved through the following technical solutions：
A kind of UV photodetector of zinc oxide-polyaniline sandwich structure, the UV photodetector are with upper and lower
Two layers of ITO electro-conductive glass is substrate, and two layers of Zinc oxide nano sheet, two layers of oxidation are provided between upper and lower two layers of ITO electro-conductive glass
One layer of polyaniline nano-line is provided between zinc nanometer sheet.
The preparation method of the UV photodetector of above-mentioned zinc oxide-polyaniline sandwich structure, comprises the following steps：
(1) ITO electro-conductive glass is sequentially placed into acetone, absolute ethyl alcohol and distilled water and is cleaned by ultrasonic 30min, and dried
It is placed in after dry on stainless steel electrode folder；Prepare Zn (NO3)2Concentration is 0.03~0.07mol/L, KCL concentration be 0.07~
The 0.12mol/L aqueous solution is as electrolyte A, using three-electrode system, using platinum plate electrode as to electrode, saturated calomel electrode
As reference electrode, it is electrochemically reacted, controls 30~60 DEG C of oxidizing temperature, oxidation voltage -0.5~-1.5V, oxidization time
10~60min；After the completion of reaction, product is taken out, with distillation water washing, after drying at room temperature, product is obtained on ITO electro-conductive glass
Zinc-oxide nano chip arrays；
(2) it is 0.1~0.2 by volume by aniline monomer solution and 1mol/L dilute acid solns:20 prepare the diluted acid of aniline
Solution B, the diluted acid are watery hydrochloric acid or dilute sulfuric acid；Again toward the ammonium persulfate solution that addition concentration is 0.1mol/L in solution B, obtain
To solution C, the volume ratio of ammonium persulfate solution and solution B is 0.5~1.0:20；Then solution C is placed in temperature as 0~4 DEG C
Refrigerator in react 0.5~4h, obtain polyaniline nano-line suspension；
(3) centrifuge after the polyaniline nano-line suspension of gained is taken out, washed with absolute ethyl alcohol, resulting solution is uniform
It is coated with step (1) gained zinc-oxide nano chip arrays and dries, obtains zinc oxide/polyaniline nano-composite material；Will
The fixed assembling face-to-face of zinc oxide/polyaniline nano-composite material of gained, that is, be made zinc oxide-polyaniline sandwich structure
UV photodetector.
The number of step (1) the distillation water washing is 2~3 times.
Step (3) number washed with absolute ethyl alcohol is 2~4 times, so as to by polyaniline nano-line suspension
Acid elution is clean, to prevent the acid corrosion zinc-oxide nano chip arrays of residual.
The present invention is had the following advantages relative to prior art and effect：
(1) synthesize the zinc-oxide nano chip arrays of pattern, size uniformity by simple and easy electrochemical process, have than
The characteristics of surface area is big, and electron transfer rate is fast, add the site of material and action of ultraviolet light so that the ultraviolet photoelectric detection
The characteristics of utensil has a stable performance, high sensitivity, and the response time is short.
(2) it is compound using polyaniline nano-line and zinc-oxide nano chip arrays, good zinc oxide-polyaniline can be formed
Heterojunction boundary, be advantageous to the separation of photo-generate electron-hole, reduce Carrier recombination probability, improve quantum efficiency.
(3) preparation method provided by the present invention is simple, and raw material is easy to get, and cost is low, and technique is simply easily realized, has fine
Development prospect and very high commercial exploitation.
Brief description of the drawings
Fig. 1 is the structural representation of zinc oxide-polyaniline sandwich structure UV photodetector, wherein 1 is ITO conductive
Glass, 2 be Zinc oxide nano sheet, and 3 be polyaniline nano-line.
Fig. 2 is the scanning electron microscope (SEM) photograph of the gained zinc-oxide nano chip arrays top surface of embodiment 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of the gained zinc oxide of embodiment 2-polyaniline nano-composite material top surface.
Fig. 4 is the scanning electron microscope (SEM) photograph of the gained zinc oxide of embodiment 2-polyaniline nano-composite material section.
Fig. 5 is the X-ray diffractogram of the gained zinc-oxide nano chip arrays of embodiment 2, and the peak of asterisk is ITO substrates in figure
Peak.
Fig. 6 is the photoelectricity test result of the gained zinc oxide of embodiment 2-polyaniline sandwich structure UV photodetector
Figure.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1~4, a kind of preparation method of the UV photodetector of zinc oxide/polyaniline sandwich structure are as follows：
(1) ITO electro-conductive glass is cut into 10mm × 20mm sizes, is sequentially placed into acetone, absolute ethyl alcohol and distilled water and surpasses
Sound cleans 30min, and stainless steel electrode folder is placed in after being baked to.Prepare Zn (NO3)2, KCL the aqueous solution as electrolyte A,
Using three-electrode system, it is electrochemically reacted using platinum plate electrode as to electrode, saturated calomel electrode as reference electrode.Instead
After the completion of answering, product is taken out, with water washing is distilled 2~3 times, after drying at room temperature, obtains product zinc-oxide nano chip arrays.
(2) aniline monomer solution and 1mol/L watery hydrochloric acid or dilution heat of sulfuric acid are prepared to dilute salt of aniline according to a certain volume
Acid or dilution heat of sulfuric acid B, then toward the oxidant ammonium persulfate solution that concentration is 0.1mol/L is added in solution B, solution C is obtained,
Solution C is placed in the refrigerator that temperature is 0~4 DEG C immediately and reacts 0.5~4h.
(3) centrifuge, washed with absolute ethyl alcohol, after being repeated 3 times, by institute after the polyaniline nano-line suspension of gained is taken out
Solution is obtained uniformly to be coated with step (1) gained zinc-oxide nano chip arrays and dry.By zinc oxide/polyaniline nano of gained
Composite assembles according to structure shown in Fig. 1 is fixed face-to-face, that is, described UV photodetector is made.
(4) products therefrom is characterized with x-ray powder diffraction instrument (XRD) and ESEM (SEM), and by after assembling
UV photodetector test its photoelectric properties with electrochemical workstation.Wherein XRD tube voltage and electric current are respectively 40kV
And 40mA.SEM be the model JSM-7001F that Amada Co., Ltd. is produced ESEM, electrochemical workstation is
Produced by Shanghai Chen Hua Instrument Ltd., model CHI660D.
The preparation condition parameter of embodiment 1~4 is as shown in the table：
Implementation result：
(1) Fig. 2~4 are the gained Zinc oxide nano sheet of embodiment 2 and the ESEM knot of zinc oxide/polyaniline composite
Fruit.As a result show, Zinc oxide nano sheet completely covers ITO substrate, and pattern is homogeneous, stable.Polyaniline nano-line and zinc oxide
Nanometer sheet combining case is good.
(2) Fig. 5 is the XRD results of the gained Zinc oxide nano sheet of embodiment 2, is as a result accredited as hexagonal wurtzite structure oxidation
Zinc.
(3) Fig. 6 is the photoelectricity test of sandwich structure zinc oxide/polyaniline UV photodetector of the gained of embodiment 2
As a result.As a result show has obvious response, high sensitivity, electric current stabilization for ultraviolet light.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
- A kind of 1. UV photodetector of zinc oxide-polyaniline sandwich structure, it is characterised in that：The UV photodetector It is using upper and lower two layers of ITO electro-conductive glass as substrate, two layers of Zinc oxide nano sheet is provided between upper and lower two layers of ITO electro-conductive glass, One layer of polyaniline nano-line is provided between two layers of Zinc oxide nano sheet.
- A kind of 2. preparation side of the UV photodetector of zinc oxide-polyaniline sandwich structure according to claim 1 Method, it is characterised in that comprise the following steps：(1) ITO electro-conductive glass is sequentially placed into acetone, absolute ethyl alcohol and distilled water and is cleaned by ultrasonic 30min, and after being baked to It is placed on stainless steel electrode folder；Prepare Zn (NO3)2Concentration is 0.03~0.07mol/L, KCL concentration is 0.07~0.12mol/L The aqueous solution as electrolyte A, using three-electrode system, using platinum plate electrode as to electrode, saturated calomel electrode is as reference Electrode, it is electrochemically reacted, 30~60 DEG C of oxidizing temperature of control, oxidation voltage -0.5~-1.5V, oxidization time 10~ 60min；After the completion of reaction, product is taken out, with distillation water washing, after drying at room temperature, product oxidation is obtained on ITO electro-conductive glass Zinc nano-chip arrays；(2) it is 0.1~0.2 by volume by aniline monomer solution and 1mol/L dilute acid solns:20 prepare the dilute acid soln of aniline B, the diluted acid are watery hydrochloric acid or dilute sulfuric acid；Again toward the ammonium persulfate solution that addition concentration is 0.1mol/L in solution B, obtain molten The volume ratio of liquid C, ammonium persulfate solution and solution B is 0.5~1.0:20；Then solution C is placed in the ice that temperature is 0~4 DEG C 0.5~4h is reacted in case, obtains polyaniline nano-line suspension；(3) centrifuged after the polyaniline nano-line suspension of gained is taken out, washed with absolute ethyl alcohol, resulting solution is uniformly coated with On step (1) gained zinc-oxide nano chip arrays and dry, obtain zinc oxide/polyaniline nano-composite material；By gained The fixed assembling face-to-face of zinc oxide/polyaniline nano-composite material, that is, the ultraviolet of zinc oxide-polyaniline sandwich structure is made Photodetector.
- 3. preparation method according to claim 2, it is characterised in that：The number of step (1) the distillation water washing for 2~ 3 times.
- 4. preparation method according to claim 2, it is characterised in that：Step (3) number washed with absolute ethyl alcohol For 2~4 times.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108899421A (en) * | 2018-06-26 | 2018-11-27 | 暨南大学 | Full-inorganic perovskite solar battery and its preparation method and application based on polyaniline and zinc oxide photoactive layers |
| CN109294229A (en) * | 2018-08-31 | 2019-02-01 | 浙江工业大学 | Composite micro-powder and the preparation method and application thereof with classification heterojunction structure |
| CN111889143A (en) * | 2020-05-08 | 2020-11-06 | 华南师范大学 | Preparation method of tin dioxide/polyaniline nanowire composite photocatalyst |
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| CN102121130A (en) * | 2011-02-17 | 2011-07-13 | 东南大学 | ZnO nano slice/nano wire composite structure with photocatalysis characteristic and preparation method thereof |
| CN102437791A (en) * | 2011-08-30 | 2012-05-02 | 东北师范大学 | Preparation method of photoinduction nano alternative-current power generator based on zinc oxide/ polyaniline/zinc oxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899421A (en) * | 2018-06-26 | 2018-11-27 | 暨南大学 | Full-inorganic perovskite solar battery and its preparation method and application based on polyaniline and zinc oxide photoactive layers |
| CN108899421B (en) * | 2018-06-26 | 2022-01-04 | 暨南大学 | All-inorganic perovskite solar cell and preparation method and application thereof |
| CN109294229A (en) * | 2018-08-31 | 2019-02-01 | 浙江工业大学 | Composite micro-powder and the preparation method and application thereof with classification heterojunction structure |
| CN111889143A (en) * | 2020-05-08 | 2020-11-06 | 华南师范大学 | Preparation method of tin dioxide/polyaniline nanowire composite photocatalyst |
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Application publication date: 20171110 |