CN109490371A - A kind of methylamine monitor and preparation method thereof - Google Patents
A kind of methylamine monitor and preparation method thereof Download PDFInfo
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- CN109490371A CN109490371A CN201811436988.0A CN201811436988A CN109490371A CN 109490371 A CN109490371 A CN 109490371A CN 201811436988 A CN201811436988 A CN 201811436988A CN 109490371 A CN109490371 A CN 109490371A
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010410 layer Substances 0.000 claims abstract description 175
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 20
- 239000002346 layers by function Substances 0.000 claims abstract description 19
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 23
- 238000004528 spin coating Methods 0.000 claims description 23
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 17
- 230000005540 biological transmission Effects 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002042 Silver nanowire Substances 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000012806 monitoring device Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IKUCKMMEQAYNPI-UHFFFAOYSA-N [Pb].CN.[I] Chemical compound [Pb].CN.[I] IKUCKMMEQAYNPI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000003956 methylamines Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 241000178435 Eliokarmos dubius Species 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- 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
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- 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
-
- 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
-
- 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
- H10K85/30—Coordination compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- 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
A kind of methylamine monitor provided by the invention and preparation method thereof, including transparent electrode layer, functional layer, metal to electrode layer and external impressed current table, wherein, transparent electrode layer, functional layer and metal stack gradually electrode layer, and transparent electrode layer, functional layer and metal are sequentially reduced the area of electrode layer；Functional layer includes electron transfer layer and perovskite active layer, wherein perovskite active layer is laminated on the electron transport layer；Methylamine can be rapidly detected by the methylamine monitor, and equipment variations are obvious, be completely superior to other conventional methylamine monitoring devices；Hole can effectively be extracted out electrode layer from calcium titanium ore bed and photoelectric current is exported to external circuit by metal simultaneously, simplified the preparation process of device, reduced the preparation cost of device.
Description
Technical field
The invention belongs to novel environment friendlies and security appliance field, and in particular to a kind of methylamine monitor and preparation method thereof.
Background technique
Methylamine is that one kind common are machine compound, chemical formula CH3NH2, it is important Organic Chemical Industry raw material, often
It is widely used the preparation in other chemicals.Methylamine has stronger bio-toxicity, has stronger penetrating odor, with
The danger such as burning, explosion then easily occur for air mixing.Since the usage amount of methylamine is very high, so if in storage and transport mistake
Without effective safety measure and source of early warning in journey, it is also easy to produce security risk.China has more ground once to report that methylamine revealed band
The environmental hazard come and the person, property loss.Therefore, can quickly the excess methylamine gas in surrounding atmosphere be produced by designing one kind
The safe early warning equipment of raw response, has greater significance.
Summary of the invention
The purpose of the present invention is to provide a kind of methylamine monitors and preparation method thereof, solve existing methylamine and are transporting
In the process without effective safety measure and source of early warning, lead to the defect that security risk easily occurs.
In order to achieve the above object, the technical solution adopted by the present invention is that:
A kind of methylamine monitor provided by the invention, including transparent electrode layer, functional layer, metal are to electrode layer and external electricity
Flow table, wherein transparent electrode layer, functional layer and metal stack gradually electrode layer, and transparent electrode layer, functional layer and gold
Category is sequentially reduced the area of electrode layer；Functional layer includes electron transfer layer and perovskite active layer, wherein perovskite active layer
Stacking is on the electron transport layer.
Preferably, the material selection of electron transfer layer is using SnO2Or TiO2；The material of perovskite active layer is
(RNH3)AXnY3-n, wherein R=alkyl；A=Pb, Sn；X, Y=Cl, Br, I；N is the real number of 0-3.
Preferably, the material that metal uses electrode layer is gold, silver, aluminium or platinum.
Preferably, transparent electrode layer, functional layer and metal are sequentially reduced the area of electrode layer；Transparent electrode layer and metal
To the positive and negative anodes for being connected separately with external ammeter on electrode layer.
Preferably, hole transmission layer is also laminated on perovskite active layer.
Preferably, barrier layer is also laminated on hole transmission layer.
A kind of preparation method of methylamine monitor, comprising the following steps:
Firstly, being dried up after transparent electrode layer is cleaned up spare；
Secondly, sequentially forming electron transfer layer, perovskite active layer and metal on transparent electrode layer to electrode layer.
Preferably, the electrode surface of transparent electrode layer is successively ultrasonically treated using deionized water, acetone, isopropanol respectively,
Then it is cleaned using ultraviolet rays cleaning machine, nitrogen stream drying is spare.
Preferably, using the tin oxide nano particle suspension that partial size is 2-20nm as spin coating liquid, on transparent electrode layer
Spin coating is carried out with the spin coating parameters of 2500-6000RPM, 40-80s, obtains the electron transfer layer of 10-40nm.
Preferably, when preparing perovskite active layer, first using DMF as solvent, the slurry containing perovskite is prepared, wherein
Containing the perovskite of 20-45% in slurry；Secondly, the spin coating parameters of 40-80s are carried out in electron transfer layer with 1000-3000rpm
Spin coating obtains perovskite active layer.
Preferably, when preparing metal to electrode layer, with the silver nanoparticle that diameter is 100-200nm, length is 50-150 μm
As raw material the metal with a thickness of 30-100nm is prepared to electrode layer, wherein scrape in line colloidal sol in the way of blade coating
The technological parameter of cutter painting cloth: temperature is that room temperature, coating speed 10-30mm/s, scraper and substrate spacing are 50 μm；After coating,
It anneals in nitrogen, annealing temperature is 75-100 DEG C, annealing time 10-20min.
Compared with prior art, the beneficial effects of the present invention are:
A kind of methylamine detector provided by the invention guides photoelectric current into external circuit, electron-transport by transparent electrode layer
Layer plays the role of connection between transparent electrode layer and perovskite active layer, and perovskite active layer is the core material of this example
Layer, play the role of monitor methylamine key core, monitor methylamine principle be, when use methylamine lead iodine as the material of this layer
When, excessive methylamine gas can react with crystallized methylamine lead iodine black thin film in atmosphere, be formed faint yellow
Bright compound MAPbI3XMA, so that the Ca-Ti ore type solar cell device failure of photoelectric conversion can be carried out originally, because
This methylamine gas can the device simultaneously occur two kinds of considerable variations: 1, the calcium titanium ore bed crystalline membrane of black becomes faint yellow
Transparent membrane, the equipment, that is, observable such as naked eyes or monitor；2, perovskite battery device fails, and external circuits such as ammeter etc. can
To monitor that photoelectric current declines to a great extent；The reaction response is rapid, and variation is obvious, is completely superior to other conventional methylamine monitoring devices；
Hole can effectively be extracted out electrode layer from calcium titanium ore bed and photoelectric current is exported to external circuit by metal, simplify device
Preparation process, reduce the preparation cost of device.
Further, electron transfer layer preparation method is easy to operate while effect is outstanding, conventional perovskite phototube
Titanium oxide electron transfer layer used in part is meso-hole structure, and material layer is thicker, material utilization amount is larger, must high temperature burning in preparation
Knot, energy consumption is high, and electron-transport effect is relatively general, and the tin oxide electron transfer layer for using the spin coating method of this example to prepare, knot
Structure is planar layer structure, and thickness only has 10-40nm, high degree reduce tin oxide dosage and subsequent calcium titanium ore bed
The dosage of active material reduces preparation cost, meanwhile, the method that this example uses can be prepared at low temperature, meet application effect
Fruit；The sharpest edges of another aspect are the stannic oxide layer energy band and transparent electrode layer and perovskite active layer with a thickness of 10-40nm
It matches the most, better plays the effect of connection and electronics conduction；
Further, select silver nanowires electrode as metal to electrode layer, there are mainly two types of advantages, one is major diameter
Silver nanowire layer more suitable than, thickness matches the most with perovskite active layer material energy level, can not select hole transmission layer
In the case where, effectively hole can be extracted out from calcium titanium ore bed and photoelectric current is exported into external circuit, simplify device
Preparation process, the preparation cost for reducing device；The second is silver nanowires electrode sheet is as loose and porous structure, to gas such as methylamines
Body has adsorption effect, while its microcosmic reticular structure can make methylamine gas relatively easily penetrate this layer realization and internal layer
Perovskite active layer is contacted, and contact area is increased, and improves reaction efficiency.
Further, using the tin oxide nano particle suspension that partial size is 2-20nm as spin coating liquid, in transparent electrode layer
On with the spin coating parameters of 2500-6000RPM, 40-80s carry out spin coating, obtain the electron transfer layer of 10-40nm；This layer is using high
Fast spin-coating method prepares planar layer structure, and layer surface, which rises and falls, is no more than 3nm, has largely evaded other routine sides
Plane layer prepares the problem of inadequate uniform ground in method, and the surface of uniform ground help to obtain property needed for this device
Matter: the i.e. interface layer of function admirable and high electron-transport efficiency；In addition, the tin oxide in (2-20nm) in this particle size range
Nanoparticle is formed by plane electronics transport layer energy level and matches the most with perovskite active layer, is conducive to electronics conduction, simultaneously
It is very low to the absorption of light and reflection effect, improves the optical absorption and photoelectric conversion efficiency of perovskite active layer；Finally,
As a whole, relatively thin tin oxide plane electronics transport layer reduces the materials'use amount of itself and subsequent calcium titanium ore bed,
The normal temperature preparation method of this layer reduces energy consumption simultaneously, meets the requirement of green, environmental protection.
Further, perovskite active layer prepares the controllable planar layer structure of thickness using high speed rotation coating method, should
Both method is similar with the condition that electron transfer layer uses, so that the interfacial effect between two planar layer structures reduces, improve
Between contact effect, conducive to the transmission of electronics；
In addition, there are some properties, size phase using perovskite active layer material of hybrid inorganic-organic itself and methylamine
As structural unit, improve the chemical affinity with methylamine molecule, methylamine gas molecule allowed rapidly to intert, combine
To among the lattice of perovskite crystal film, it is effectively formed compound, makes the discoloration failure of perovskite active layer, to reach first
The effect of amine monitoring；
On the other hand, the material crystalline of this layer is black, and in conjunction with methylamine molecule after be it is nearly transparent faint yellow, two
Person's color difference is very big, is very easy to identification, meanwhile, this layer material can generate higher photoelectric current in normal state, and with
After methylamine combines, since material itself and methylamine molecule compatibility are best, chemical reaction can quickly occur and generate corresponding crystal
The variation of structure, photoelectric current can rapidly, appreciably decline, and realize the highly sensitive monitoring of methylamine.
Detailed description of the invention
Fig. 1 is the schematic illustration of methylamine monitor of the present invention；
Wherein, 1, transparent electrode layer 2,3. metal of functional layer are to electrode layer 4, external impressed current table.
Specific embodiment
When describing embodiment of the present invention, for the sake of clarity, specific term has been used；However, the present invention without
Meaning is confined to selected specific term；It should be appreciated that each particular element includes that similar method is run to realize similar purpose
All technically equivalent ones.
Ca-Ti ore type semiconductor material methylamine lead iodine (chemical formula CH3NH3PbI3Namely MAPbI3) it is the current novel sun
Star's material in energy battery has the characteristics that material is cheap, preparation is simple, photoelectric conversion capacity is strong, in the course of the research
It was found that excessive methylamine gas can react with crystallized methylamine lead iodine black thin film in atmosphere, formed light
The compound MAPbI of yellow transparent3XMA, so that the Ca-Ti ore type solar cell device of photoelectric conversion can be carried out originally
Failure, meanwhile, the chemical reaction is very sensitive, and reaction speed is very fast, is suitable for being monitored the expansion application in terms of sensor.
Therefore, the cardinal principle of technical method used in this patent are as follows: utilize the simplification constructed on the transparent electrodes
Ca-Ti ore type electrooptical device, by a part of active material MAPbI3Layer is exposed in air, when the first for having leakage in air
It, will be with MAPbI in the presence of amine gas3Chemically react: 1, the calcium titanium ore bed crystalline membrane of black becomes pale yellow transparent
Film, the equipment, that is, observable such as naked eyes or monitor；2, perovskite battery device fails, and external circuits such as ammeter etc. can supervise
Photoelectric current is measured to decline to a great extent.The two phenomenons have the characteristics that observation is convenient, it is rapid to respond, and are suitable for carrying out environmental protection and safety
Monitoring.
The present invention is described in further detail with reference to the accompanying drawing.
As shown in Figure 1, a kind of methylamine monitor provided by the invention, including transparent electrode layer 1, functional layer 2, metal are to electricity
Pole layer 3 and external impressed current table 4, wherein transparent electrode layer 1, functional layer 2 and metal are sequentially overlapped electrode layer 3, meanwhile, it is external
The positive and negative anodes of ammeter 4 respectively connect electrode layer 3 and transparent electrode layer 1 with metal.
Wherein, transparent electrode layer 1 is using the substrate of glass for being deposited with transparent electrode, the transparent electrode be ITO,
FTO or AZO, area is unlimited, and (the present embodiment is 3 × 3cm using size2)；It is preferable to use common ITO, FTO, AZO
Deng the conduct substrate such as flexibility PET, rigid high transparent glass, which can be selected, to be prepared and is applied, so that the application of the methylamine monitor
Range and application scenarios are expanded.Its energy level is after the special moditied processing to material itself (for ITO, that is, indium oxide
Tin can adjust its energy band by adjusting its tin dope degree, as tin dope be 5%-10% when, obtained transparent electrode layer
It is more appropriate), it more can SnO in matching feature layer2、TiO2Energy level so that electric current transmission it is more smoothly, extend the inspection of device
Survey range.
Before use, should by electrode surface successively respectively using deionized water, acetone, isopropanol be ultrasonically treated 15 minutes,
Then it is cleaned 10 minutes using ultraviolet rays cleaning machine, nitrogen stream drying is spare.
Functional layer 2 includes double-layer structure, and first layer is electron transfer layer, using atomic deposition, vapor deposition, magnetron sputtering
Or spin-coating method is prepared；In the present embodiment, electron transfer layer is using SnO2Or TiO2,
Particularly, the solution spin coating method that the present invention uses prepares the layer, the tin oxide nano that can be 2-20nm by partial size
Particle suspension directly as spin coating liquid, in transparent electrode layer substrate with the spin coating parameters of 2500-6000RPM, 40-80s into
The preparation of row different-thickness stannic oxide layer (10-40nm),
Particularly, the present invention obtains the stannic oxide layer that thickness is about 30nm using the spin coating parameters of 3000RPM, 60s；
The second layer is the perovskite active layer prepared on the electron transport layer, and the structure of material is (RNH3)AXnY3-n(R
=alkyl；A=Pb, Sn；X, Y=Cl, Br, I；N is the real number of 0-3), it is preferable to use CH3NH3PbI3(i.e. MAPbI3), usually adopt
It is formed with the methods of spin-coating method, vapor deposition, magnetron sputtering.
Particularly, using DMF as solvent, the slurry containing perovskite is prepared, wherein containing the perovskite of 20-45% in slurry；It is excellent
Select the perovskite in slurry containing 35%；With 1000-3000rpm in substrate, the spin coating parameters of 40-80s carry out 500-700nm not
It is prepared by the calcium titanium ore bed of stack pile,
Particularly, using 2000rpm, the spin coating parameters of 60s can obtain the calcium titanium ore bed with a thickness of 600nm, then pass through
Preferably 120 DEG C, the calcium titanium ore bed film of black can be obtained in 90-150 DEG C of annealing 30min.
After the completion of the preparation of functional layer 2, part of functions layer can be struck off with scraper, in the present embodiment, the area of removing
For uses such as 0.5cm, the standby connection external impressed current tables 4 of transparent electrode ITO layer of exposed portion.
Meanwhile can also add one layer of hole transmission layer on perovskite active layer, the material that hole transmission layer uses is usually
Cuprous rhodanide, cuprous iodide, PTAA, spiro-OMeTAD, PEDOT:PSS, it acts as preferably by hole from perovskite
It is exported in active layer to metal in electrode layer, i.e. electron transfer layer-perovskite active layer-hole transmission layer 3-tier architecture；
Meanwhile can also add one layer of barrier layer on above-mentioned hole transmission layer, the material of barrier layer is usually carbon fiber, graphite
Alkene, reduced graphene oxide serving adjust energy level it acts as further, optimize hole transport, while reducing metal to electrode layer
Corrosion and osmotic effect to hole transmission layer, i.e. electron transfer layer-perovskite active layer -4 layers of hole transmission layer-barrier layer knot
Structure.
It is significant to note that if thickness must sufficiently small while area using hole transmission layer and barrier layer
Should be smaller than perovskite active layer, reduce the contact for interfering perovskite active layer with methylamine gas to the greatest extent；And the excellent of above-mentioned layer is added
Gesture is, improves photoelectric current in normal state so that device contact methylamine gas failure after electric current variation more
To be obvious, while improving the durability of device.
Thermal evaporation, magnetron sputtering, atom can be used for metals such as gold, silver, aluminium, platinum in the material that metal uses electrode layer 3
The preparation of the methods of deposition, laser deposition can also use roll-to-roll process to be prepared, i.e., by conductive gold during the preparation process
The slurry for belonging to electrode material passes through the side such as slot coated, blade coating, silk-screen printing, intaglio printing, ink-jet application, ink jet printing
Method is formed.
It particularly, is 100-200nm with diameter, 50-150 μm of length of silver nanowires colloidal sol is prepared dense as raw material
Spend the aqueous isopropanol of 20g/L；Metal is prepared to electrode layer using knife coating method, wherein the technological parameter of blade coating:
Blade coating speed is 10-30mm/s, preferably 20mm/s；Coating temperature is room temperature；Scraper and substrate spacing are 50 μm；Coating
Afterwards, it is made annealing treatment in nitrogen, annealing temperature is 75-100 DEG C, and annealing time is 10-20 minutes, and preferably annealing temperature is
90 DEG C, annealing time is 15 minutes, obtains the metal with a thickness of 30-100nm to electrode layer.
Resulting metal should be less than functional layer 2 to the area of electrode layer, as shown in Figure 1, so that partial function layer is exposed to
Air, encountering methylamine using perovskite, to become the principle of pale yellow transparent film by black thin film pre- come the instruction for carrying out methylamine
It is alert；In addition, since using metal nanometer line, to electrode, more loose structure is easy to the small molecules such as methylamine in this example
It crosses, reacts conducive to it with internal calcium titanium ore bed.
Transparent electrode layer 1 and metal are connected to the external impressed current table 4 of electrode layer 3: for monitoring and indicating that the device generates
Photoelectric current size, range can be that positive and negative electrode with the presence of commercially produced product need to be only connected to 1 layer by 1-1000mA in this example
With 3 layers, the suitable multimeter of range also can be used and replace.
Working principle are as follows: under continual and steady light source irradiation, external impressed current table 4 can monitor the stabilization that the device generates
Photoelectric current can react in the presence of having a large amount of methylamine gas in atmosphere with exposed calcium titanium ore bed, except film changes colour
Outside, sharp fall simultaneously is shown as the photoelectric current that external impressed current table 4 monitors and is decreased obviously by photoelectric conversion efficiency.
Claims (10)
1. a kind of methylamine monitor, which is characterized in that including transparent electrode layer, functional layer, metal to electrode layer and external impressed current
Table, wherein transparent electrode layer, functional layer and metal stack gradually electrode layer；Functional layer includes electron transfer layer and calcium
Titanium ore active layer, wherein perovskite active layer is laminated on the electron transport layer.
2. a kind of methylamine monitor according to claim 1, which is characterized in that the material selection of electron transfer layer is to adopt
Use SnO2Or TiO2；The material of perovskite active layer is (RNH3)AXnY3-n, wherein R=alkyl；A=Pb, Sn；X, Y=Cl,
Br, I；N is the real number of 0-3.
3. a kind of methylamine monitor according to claim 1, which is characterized in that the material that metal uses electrode layer for
Gold, silver, aluminium or platinum.
4. a kind of methylamine monitor according to claim 1, which is characterized in that transparent electrode layer, functional layer and metal pair
The area of electrode layer is sequentially reduced；Transparent electrode layer and metal are to the positive and negative anodes for being connected separately with external ammeter on electrode layer.
5. a kind of methylamine monitor according to claim 1, which is characterized in that be also laminated with hole on perovskite active layer
Transport layer.
6. a kind of methylamine monitor according to claim 5, which is characterized in that be also laminated with barrier on hole transmission layer
Layer.
7. a kind of preparation method of methylamine monitor, which comprises the following steps:
Firstly, being dried up after transparent electrode layer is cleaned up spare；
Secondly, sequentially forming electron transfer layer, perovskite active layer and metal on transparent electrode layer to electrode layer.
8. a kind of preparation method of methylamine monitor according to claim 7, which is characterized in that the electrode of transparent electrode layer
Surface is successively ultrasonically treated using deionized water, acetone, isopropanol respectively, is then cleaned using ultraviolet rays cleaning machine, nitrogen
Air-flow drying is spare.
9. a kind of preparation method of methylamine monitor according to claim 7, which is characterized in that by partial size be 2-20nm
Tin oxide nano particle suspension is as spin coating liquid, with the spin coating parameters of 2500-6000RPM, 40-80s on transparent electrode layer
Spin coating is carried out, the electron transfer layer of 10-40nm is obtained；
When preparing perovskite active layer, first using DMF as solvent, the slurry containing perovskite is prepared, wherein contain 20- in slurry
45% perovskite；Secondly, the spin coating parameters of 40-80s carry out spin coating in electron transfer layer with 1000-3000rpm, calcium is obtained
Titanium ore active layer.
10. a kind of preparation method of methylamine monitor according to claim 7, which is characterized in that preparing metal to electricity
When the layer of pole, using diameter is 100-200nm, length is 50-150 μm silver nanowires colloidal sol as raw material, blade coating is utilized
The metal with a thickness of 30-100nm is prepared to electrode layer in mode, wherein the technological parameter of blade coating: temperature be room temperature,
Coating speed is 10-30mm/s, scraper and substrate spacing are 50 μm；It after coating, anneals in nitrogen, annealing temperature is
75-100 DEG C, annealing time 10-20min.
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