CN112563420A - Solar blind ultraviolet perovskite photoelectric detector and preparation method thereof - Google Patents
Solar blind ultraviolet perovskite photoelectric detector and preparation method thereof Download PDFInfo
- Publication number
- CN112563420A CN112563420A CN202011457667.6A CN202011457667A CN112563420A CN 112563420 A CN112563420 A CN 112563420A CN 202011457667 A CN202011457667 A CN 202011457667A CN 112563420 A CN112563420 A CN 112563420A
- Authority
- CN
- China
- Prior art keywords
- layer
- perovskite
- conductive glass
- blind ultraviolet
- metal electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000010408 film Substances 0.000 claims description 18
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 14
- 239000002096 quantum dot Substances 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 12
- 230000005525 hole transport Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- -1 terbium-activated magnesium aluminate Chemical class 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- QWANGZFTSGZRPZ-UHFFFAOYSA-N aminomethylideneazanium;bromide Chemical compound Br.NC=N QWANGZFTSGZRPZ-UHFFFAOYSA-N 0.000 claims description 4
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012296 anti-solvent Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001723 curing Methods 0.000 claims description 2
- DXNVUKXMTZHOTP-UHFFFAOYSA-N dialuminum;dimagnesium;barium(2+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Mg+2].[Al+3].[Al+3].[Ba+2].[Ba+2] DXNVUKXMTZHOTP-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 2
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 15
- 230000004044 response Effects 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000825 ultraviolet detection Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910003363 ZnMgO Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- H10K30/87—Light-trapping means
-
- 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
- H10K85/00—Organic materials used in the body or electrodes of 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
The invention belongs to the technical field of solar blind photoelectric detection, and particularly relates to a solar blind ultraviolet perovskite photoelectric detector and a preparation method thereof. The solar blind ultraviolet perovskite photoelectric detector is sequentially provided with a filter layer, a lower conversion light-emitting window layer, a conductive glass layer, a perovskite photosensitive layer and a metal electrode layer along the light entering direction, wherein the lower conversion light-emitting window layer can convert solar blind ultraviolet light into fluorescence, and the perovskite photosensitive layer can convert the fluorescence into an electric signal. According to the invention, the perovskite visible light detector and the lower conversion window layer are integrated, solar blind ultraviolet light is firstly absorbed by the lower conversion layer film and then converted into visible fluorescence, and then the visible fluorescence is captured by the perovskite visible light detector and converted into an electric signal to be exported, so that the spectral response limitation of the traditional perovskite material is effectively overcome, and the perovskite visible light conversion window has a wide market application prospect.
Description
Technical Field
The invention belongs to the technical field of solar blind photoelectric detection, and particularly relates to a solar blind ultraviolet perovskite photoelectric detector and a preparation method thereof.
Background
Ultraviolet photodetectors have numerous applications in civilian and military applications, such as biological, chemical analysis, flame sensing, covert air-to-air communications, missile tracking, and environmental monitoring, to name a few. Because ozone and water vapor particles in the atmosphere have extremely strong absorption to deep ultraviolet light, solar radiation with the wavelength shorter than 280nm hardly exists on the earth surface, and the section of light is called a solar blind area. Because the natural background of the solar dead zone is low, the photoelectric detector working in the spectrum range has the advantages of high signal-to-noise ratio, low false alarm rate and the like. Commercially available solar blind detectors are typically photomultiplier tubes that are bulky and fragile and require large bias voltages, limiting their use. Solar blind photodetectors based on wide-bandgap semiconductor materials (diamond, gallium oxide, GaAlN, ZnMgO, etc.) have the advantages of high radiation intensity, inherent solar blind absorption, etc., and are considered as potential substitutes for photomultiplier tubes. However, the substrate required for manufacturing such solar blind ultraviolet photodetectors is expensive, and the manufacturing cost of high-performance devices remains high due to the vacuum coating processes such as MOCVD (metal organic chemical vapor deposition), MBE (molecular beam epitaxy), PLD (pulsed laser deposition), magnetron sputtering and the like adopted in the process. In addition, when the solar blind photodetector based on the wide bandgap semiconductor material works, a higher bias voltage is required to be externally connected to promote the transportation of photon-generated carriers, so that the electric energy loss is larger.
In 2009, organic-inorganic metal hybrid perovskite materials appear in the photoelectric field as a new generation of photoreceivers with great potential, and the research of perovskite photoelectric devices is drawn. Owing to the excellent photoconduction, adjustable forbidden band, high absorption coefficient, low exciton combination energy and other advantages of perovskite material, the organic-inorganic hybrid perovskite material can show fast photoresponse characteristic when excited by light and is ideal material for high performance photoelectric detector. The perovskite photoelectric detector reported at present is obviously superior to an organic photoelectric detector and a quantum dot photoelectric detector in the aspects of sensitivity, dynamic range, response speed and the like, and becomes a current research hotspot. In addition, the perovskite-based core photoelectric conversion material has the characteristics of low price and solution preparation, is convenient to prepare by adopting a roll-to-roll technology without vacuum conditions, and provides possibility for large-scale and low-cost manufacture of perovskite photoelectric detectors.
However, due to the influence of forbidden bandwidth, the photoelectric conversion range of the perovskite photosensitive material is generally between 350nm and 800nm, and the responsivity to solar blind ultraviolet light is low, so that the development of solar blind ultraviolet perovskite photodetectors is hindered.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the solar blind ultraviolet perovskite photoelectric detector. The novel solar blind ultraviolet perovskite photoelectric detector can effectively overcome the spectral response limitation of the traditional perovskite material, and can realize high-performance self-driven solar blind ultraviolet detection while the material cost is low and the process is simple. The detailed technical scheme of the invention is as follows.
In order to achieve the above object, according to one aspect of the present invention, there is provided a solar blind ultraviolet perovskite photoelectric detector, wherein a filter layer, a down-conversion light emitting window layer, a conductive glass layer, a perovskite photosensitive layer and a metal electrode layer are sequentially disposed along an entrance direction of light, the filter layer controls light with a wavelength of 200-.
The conductive glass layer, the perovskite photosensitive layer and the metal electrode layer form a perovskite visible light detector, and fluorescence can be captured and converted into an electric signal to be led out.
Preferably, the down-conversion luminescence window layer is a perovskite quantum dot or a three-primary-color phosphor thin film, and preferably, the perovskite quantum dot is CsPbCl3、CsPb(Cl/Br)3、CsPbBr3、FAPbBr3、CsPb(Br/I)3、CsPbI3One of the quantum dots, the three primary colors phosphor is cerium and terbium activated magnesium aluminate green powder (CeMgAl)11O19Tb), europium activated magnesium barium aluminate blue powder (BaMgAl)10O17Eu) and europium-activated yttrium oxide (Red powder Y)2O3Eu).
Preferably, the perovskite photosensitive layer is prepared by crystallizing and annealing a perovskite precursor, and the perovskite precursor is lead iodide (PbI)2) And methyl amine iodide (CH)3NH3I) Mixture, lead iodide (PbI)2) And methyl amine bromide (CH)3NH3Br) mixture, lead bromide (PbBr)2) And methyl amine bromide (CH)3NH3Br) mixture, lead bromide (PbBr)2) And methyl amine iodide (CH)3NH3I) Mixture, lead iodide (PbI)2) And formamidine hydroiodide (HC (NH)2)2I) Mixture, lead iodide (PbI)2) And formamidine hydrobromide (HC (NH)2)2Br) mixture, lead bromide (PbBr)2) And formamidine hydroiodide (HC (NH)2)2I) Mixture, lead bromide (PbBr)2) And formamidine hydrobromide (HC (NH)2)2Br) is dissolved in a mixed solution of an organic solvent.
Preferably, the conductive glass layer comprises a glass substrate and a conductive film, the conductive film is positioned on one side of the perovskite photosensitive layer, and the conductive glass layer is one of ITO conductive glass, FTO conductive glass and AZO conductive glass.
Preferably, the perovskite photosensitive layer is a perovskite photosensitive layer, and the hole transport layer is preferably polyethylene dioxythiophene-polystyrene sulfonate (PEDOT: PSS) or poly (4-phenyl) (2,4, 6-trimethylphenyl) amine (PTAA).
Preferably, the perovskite type solar cell further comprises an electron transport layer, wherein the electron transport layer is arranged between the perovskite photosensitive layer and the metal electrode layer, and is a fullerene derivative (PCBM) or carbon 60 (C)60)。
Preferably, the electron transport layer further comprises a barrier layer, the barrier layer is arranged between the electron transport layer and the metal electrode layer, and the barrier layer is 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP) or molybdenum trioxide (MoO)3)。
Preferably, the packaging layer is arranged on the surface of the metal electrode layer and used for isolating air from entering the metal electrode layer.
According to another aspect of the present invention, there is provided a method for preparing the solar blind ultraviolet perovskite photodetector described above, comprising the steps of:
(1) cleaning the conductive glass layer, and sequentially preparing a hole transport layer, a perovskite photosensitive layer, an electron transport layer, a barrier layer and a metal electrode layer on one side of the conductive film of the conductive glass layer, wherein the hole transport layer, the perovskite photosensitive layer, the electron transport layer and the barrier layer are prepared in a coating mode, and the metal electrode layer is deposited in a vacuum thermal evaporation mode;
(2) preparing a down-conversion luminescence window layer on a glass substrate of the conductive glass layer, coating perovskite quantum dots or tricolor fluorescent powder on the glass substrate, and heating and curing;
(3) and packaging the surface of the metal electrode layer to form a packaging layer, directly coupling the down-conversion light-emitting window layer with the optical filter, sealing and integrating by adopting polydimethylsiloxane, and leading out a double-electrode wire of the device, thus obtaining the solar blind ultraviolet perovskite photoelectric detector.
Preferably, the preparation method of the perovskite photosensitive layer comprises the following steps:
(s1) preparing a perovskite precursor, and adding PbI2And CH3NH3I is dissolved in a mixed solution of DMF and DMSO by heating and stirring according to the molar ratio of (1-2) to (1-2), PbI2The concentration is 1-1.5 mol/mL;
(s2) coating, namely, dropwise adding 50-100 mu L of perovskite precursor on the surface of the conductive glass layer by using a liquid-transferring gun, spin-coating to form a film, and after 5-10 s of dropwise addition, dropwise adding 150-200 mu L of chlorobenzene antisolvent on the surface of a rotating film-forming area to promote rapid crystallization of the perovskite film to obtain a primary product;
(s3) annealing at N2Under the protection of the above, annealing the primary product on a heating table at 100-120 ℃ for 10-15 min, and after the annealing is finished, the perovskite photosensitive layer is obtained.
Overall, the beneficial effects of the invention are as follows:
(1) the perovskite photosensitive material is generally in a photoelectric conversion range of 350-800 nm due to the influence of forbidden bandwidth, and has low responsivity to solar blind ultraviolet light.
(2) The perovskite visible light detector is formed by the conductive glass layer, the perovskite photosensitive layer and the metal electrode layer, fluorescence can be captured and converted into electric signals to be led out, the sensitivity is high in the visible light range, the yield of fluorescence quanta of the lower conversion window layer based on perovskite quantum dots or tricolor fluorescent powder is high, and the combination of the perovskite quantum dots or the tricolor fluorescent powder can realize high-performance solar blind ultraviolet detection at the same time of low material cost and simple process.
(3) According to the invention, the lower conversion window layer is directly coupled with one side of the ITO of the perovskite visible light detector, so that the fluorescence attenuation can be greatly reduced, and the effectiveness of solar blind deep ultraviolet detection is ensured.
(4) The device is sealed by the UV curing adhesive and PDMS, so that moisture in the air can be effectively prevented from entering the structure and decomposing the perovskite photosensitive layer and the down-conversion light-emitting window layer, and the stability of the device is guaranteed.
Drawings
FIG. 1 is a schematic structural diagram of a solar blind ultraviolet perovskite photodetector of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A solar blind ultraviolet perovskite photoelectric detector is prepared by the following method:
(1) and (3) treating a conductive glass layer, wherein the conductive glass layer is ITO conductive glass, soaking the laser-etched ITO in deionized water added with a cleaning agent, ultrasonically cleaning for 15 minutes, taking out, rinsing twice with the deionized water, ultrasonically cleaning for 15 minutes by respectively adopting acetone and ethanol, blow-drying by using a nitrogen gun, and treating for 20 minutes by using an ultraviolet ozone cleaning machine to perform surface modification.
(2) Preparing a perovskite photosensitive layer: will PbI2And CH3NH3I is dissolved in a mixed solution of DMF and DMSO with the volume ratio of 4:1 in a molar ratio of 1:1, and PbI2The concentration is 1mol/mL, and the mixture is filled with N2Heating and stirring for 2 hours in a glove box until the solute is fully dissolved, and finishing the preparation of the perovskite precursor; dripping 50 μ L of perovskite precursor on the surface of ITO substrate conductive film by using a liquid-transferring gun, spin-coating for 5s, dripping 150 μ L of chlorobenzene antisolvent on the surface of rotating sample to promote rapid crystallization of perovskite film, and annealing 1 on a heating table at 100 deg.C after spin-coatingAnd (5) 0min, and obtaining the perovskite photosensitive layer after the annealing is finished.
(3) Preparing metal electrode layer, depositing metal Ag electrode layer by vacuum thermal evaporation with vacuum degree of 0.9 × 10-4Pa, setting the current to be 140A, controlling the thickness to be 80nm, and monitoring the thickness of the film by using a film thickness meter with a crystal oscillator plate;
(4) preparing a lower conversion window layer by adding 20mg/mL CsPbBr3Dropping and coating a perovskite quantum dot toluene solution to form a film, and drying on a hot plate at 50 ℃;
(5) the preparation and packaging of the optical filter cover the packaged glass sheet, and the optical filter is sealed by adopting UV curing glue, so that moisture in the air is prevented from entering the structure and decomposing the perovskite photosensitive layer, the lower conversion window layer is directly bonded with the optical filter and coupled into a whole, PDMS is used for sealing and integration, double electrode wires of the device are led out, one electrode wire is connected with the metal electrode, and the other electrode wire is connected with the conductive film of the ITO conductive glass. The filter layer controls light with the wavelength of 200 nm and 280nm to pass through.
Example 2
This example is different from example 1 in that a hole transport layer is added, and the step (6) is located between steps (1) and (2) in example 1, as described below.
(6) Preparation of hole transport layer: PSS as a hole transport material, and spin-coating to the surface of the ITO conductive film substrate by a spin coater with the program set at 5000rpm for 30s, and then annealing on a heating table at 100 ℃ for 10min with the thickness controlled to be 20 nm.
And continuously preparing the perovskite photosensitive layer on the surface of the hole transport layer.
Example 3
This example differs from example 1 in that the preparation of the electron transport layer in step (7) and the preparation of the barrier layer in step (8) are added, and step (7) and step (8) are located between step (2) and step (3), as described below.
(7) Preparation of an electron transport layer: PCBM in chlorobenzene (15mg mL)-1) Spin coating on the surface of the perovskite thin film by a spin coater, and setting the program of the spin coater2000rpm, spin coating for 30 s. After the spin coating was completed, annealing was performed on a heating stage at 100 ℃ for 10 min.
(8) Preparation of a barrier layer: 0.5mg mL of-1The isopropanol solution of BCP was spin coated on the surface of the PCBM film by a spin coater programmed at 5000rpm for 60 seconds. After completion, drying was carried out at room temperature for 2 hours.
And (3) depositing a metal electrode layer on the surface of the barrier layer.
The examples were tested. Examples 1-3 were tested.
1. And (3) sensitivity test, specifically, sensitivity @265 nm: the ratio of the response current of the detector to the optical power under the 265nm ultraviolet illumination has the formula:
wherein, I is the response current of the detector, and P is the optical power.
2. And (3) testing the detection rate: the signal-to-noise ratio per unit incident optical power is given by the formula:
wherein R is sensitivity, e is elementary charge, JdIs the dark current (the output current of the detector in the dark state).
3. Linear dynamic range test: the range of the linear relation between the output photocurrent of the detector and the input optical power is as follows:
wherein P ishighAnd PlowRespectively the highest and lowest optical powers at which the detector output photocurrent can be linearly related to the input optical power.
4. Response rate testing: when there is a step light input, the time required for the detector output current to rise to a steady value or fall to a pre-illumination value. Generally defined as the time for the photocurrent to rise to a steady state value of 90% is the rising response rate and the time to fall to a steady state value of 10% is the falling response rate. The step light signal can be provided by a signal generator, and the photocurrent can be collected by a digital source meter or an oscilloscope.
5. And (3) testing the working voltage: the detector needs external bias voltage when working normally.
The test results are shown in table 1.
TABLE 1 test results table
According to the test results, the perovskite visible light detector and the lower conversion window layer are integrated in the embodiments 1-3, solar blind ultraviolet light is firstly absorbed by the lower conversion layer film and then converted into visible fluorescence, and the visible fluorescence is captured by the perovskite visible light detector and converted into an electric signal to be led out, so that the spectral response limitation of the traditional perovskite material is effectively overcome. The perovskite visible light detector has high sensitivity in a visible light range, the lower conversion window layer fluorescence quantum yield of perovskite quantum dots or tricolor fluorescent powder is high, and the combination of the perovskite visible light detector and the tricolor fluorescent powder can realize the low-cost high-efficiency detection of solar blind ultraviolet light. The working voltage is 0V, which shows that the prepared solar blind ultraviolet perovskite photoelectric detector inherits the advantage of photovoltaic self-driving of the perovskite visible light detector, external bias voltage is not needed during working, and the electric energy consumption of the optical detection system can be reduced.
Further, as is clear from examples 2 and 3, the use of the hole transport layer, the electron transport layer, and the blocking layer can further improve the detection performance such as the detectivity, the linear dynamic range, and the response rate.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The solar blind ultraviolet perovskite photoelectric detector is characterized in that a filter layer, a lower conversion light emitting window layer, a conductive glass layer, a perovskite photosensitive layer and a metal electrode layer are sequentially arranged along the light entering direction, solar blind ultraviolet light can be converted into fluorescence through the lower conversion light emitting window layer, and the perovskite photosensitive layer can convert the fluorescence into an electric signal.
2. The photodetector of claim 1, wherein the down-conversion luminescent window layer is a perovskite quantum dot or a tricolor phosphor thin film, preferably, the perovskite quantum dot is CsPbCl3、CsPb(Cl/Br)3、CsPbBr3、FAPbBr3、CsPb(Br/I)3、CsPbI3And one of the quantum dots, wherein the three-primary-color fluorescent powder is one of cerium, terbium-activated magnesium aluminate green powder, europium-activated magnesium barium aluminate blue powder and europium-activated yttrium oxide.
3. The photodetector of claim 2, wherein the perovskite photosensitive layer is prepared by crystallizing and annealing a perovskite precursor, and the perovskite precursor is a mixed solution of lead iodide and methyl amine iodide mixture, lead iodide and methyl amine bromide mixture, lead bromide and methyl amine iodide mixture, lead iodide and formamidine hydroiodide mixture, lead iodide and formamidine hydrobromide mixture, lead bromide and formamidine hydroiodide mixture, and lead bromide and formamidine hydrobromide mixture dissolved in an organic solvent.
4. The photodetector of claim 3, wherein the conductive glass layer comprises a glass substrate and a conductive film on one side of the perovskite photoactive layer, the conductive glass layer being one of ITO conductive glass, FTO conductive glass, and AZO conductive glass.
5. The photodetector of claim 1 or 2, further comprising a hole transport layer between the conductive glass layer and the perovskite photoactive layer, preferably a polyethylenedioxythiophene-polystyrene sulfonate or poly (4-phenyl) (2,4, 6-trimethylphenyl) amine.
6. The photodetector of claim 5, further comprising an electron transport layer disposed between the perovskite photoactive layer and the metal electrode layer, the electron transport layer being a fullerene derivative or carbon 60.
7. The photodetector of claim 1, further comprising a barrier layer disposed between the electron transport layer and the metal electrode layer, wherein the barrier layer is 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline or molybdenum trioxide.
8. The photodetector of claim 1, further comprising an encapsulation layer, wherein the encapsulation layer is disposed on the surface of the metal electrode layer and isolates air from entering the metal electrode layer.
9. The method for preparing a solar-blind ultraviolet perovskite photodetector as claimed in any one of claims 1 to 8, comprising the steps of:
(1) cleaning the conductive glass layer, and sequentially preparing a hole transport layer, a perovskite photosensitive layer, an electron transport layer, a barrier layer and a metal electrode layer on one side of the conductive film of the conductive glass layer, wherein the hole transport layer, the perovskite photosensitive layer, the electron transport layer and the barrier layer are prepared in a coating mode, and the metal electrode layer is deposited in a vacuum thermal evaporation mode;
(2) preparing a down-conversion luminescence window layer on a glass substrate of the conductive glass layer, coating perovskite quantum dots or tricolor fluorescent powder on the glass substrate, and heating and curing;
(3) and packaging the surface of the metal electrode layer to form a packaging layer, connecting the down-conversion light-emitting window layer with the optical filter, sealing and integrating by adopting polydimethylsiloxane, and leading out a double-electrode wire of the device, thus obtaining the solar-blind ultraviolet perovskite photoelectric detector.
10. The method for fabricating a solar-blind ultraviolet perovskite photodetector as claimed in claim 9, wherein the method for fabricating the perovskite photosensitive layer comprises the steps of:
(s1) preparing a perovskite precursor, and adding PbI2And CH3NH3I is dissolved in a mixed solution of DMF and DMSO by heating and stirring according to the molar ratio of (1-2) to (1-2), PbI2The concentration is 1-1.5 mol/mL;
(s2) coating, namely, dropwise adding 50-100 mu L of perovskite precursor on the surface of the conductive glass layer by using a liquid-transferring gun, spin-coating to form a film, and after 5-10 s of dropwise addition, dropwise adding 150-200 mu L of chlorobenzene antisolvent on the surface of a rotating film-forming area to promote rapid crystallization of the perovskite film to obtain a primary product;
(s3) annealing at N2Under the protection of the above, annealing the primary product on a heating table at 100-120 ℃ for 10-15 min, and after the annealing is finished, the perovskite photosensitive layer is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011457667.6A CN112563420A (en) | 2020-12-11 | 2020-12-11 | Solar blind ultraviolet perovskite photoelectric detector and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011457667.6A CN112563420A (en) | 2020-12-11 | 2020-12-11 | Solar blind ultraviolet perovskite photoelectric detector and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112563420A true CN112563420A (en) | 2021-03-26 |
Family
ID=75062196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011457667.6A Pending CN112563420A (en) | 2020-12-11 | 2020-12-11 | Solar blind ultraviolet perovskite photoelectric detector and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112563420A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113346021A (en) * | 2021-04-12 | 2021-09-03 | 西安电子科技大学 | One kind contains (BA)2Cs5Pb6Cl19Visible light blind ultraviolet detector for perovskite layer and preparation method thereof |
| CN113809239A (en) * | 2021-08-25 | 2021-12-17 | 佛山仙湖实验室 | Perovskite thin film and anti-solvent preparation method of photoelectric detector containing perovskite thin film |
| CN114958336A (en) * | 2022-04-13 | 2022-08-30 | 香港理工大学深圳研究院 | Perovskite quantum dot, deep ultraviolet photoelectric detector and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937972A (en) * | 2010-08-06 | 2011-01-05 | 浙江大学 | Organic near-ultraviolet/deep-ultraviolet double-waveband ultraviolet-light detecting device and manufacturing method thereof |
| CN108489605A (en) * | 2018-03-01 | 2018-09-04 | 南京邮电大学 | Solar blind UV detection device |
| CN109935608A (en) * | 2019-03-04 | 2019-06-25 | 东南大学 | A kind of day blind ultraviolet detection structure and preparation method thereof introducing quantum dot |
| CN110299452A (en) * | 2019-06-28 | 2019-10-01 | 北京大学深圳研究生院 | A kind of perovskite UV photodetector and preparation method thereof |
| CN110931642A (en) * | 2019-11-29 | 2020-03-27 | 南昌大学 | Ultraviolet light detector of two-dimensional perovskite single crystal and preparation method thereof |
| CN111192960A (en) * | 2018-11-14 | 2020-05-22 | 苏州大学 | Ultraviolet-visible light dual-band photoelectric detector and preparation method thereof |
-
2020
- 2020-12-11 CN CN202011457667.6A patent/CN112563420A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937972A (en) * | 2010-08-06 | 2011-01-05 | 浙江大学 | Organic near-ultraviolet/deep-ultraviolet double-waveband ultraviolet-light detecting device and manufacturing method thereof |
| CN108489605A (en) * | 2018-03-01 | 2018-09-04 | 南京邮电大学 | Solar blind UV detection device |
| CN111192960A (en) * | 2018-11-14 | 2020-05-22 | 苏州大学 | Ultraviolet-visible light dual-band photoelectric detector and preparation method thereof |
| CN109935608A (en) * | 2019-03-04 | 2019-06-25 | 东南大学 | A kind of day blind ultraviolet detection structure and preparation method thereof introducing quantum dot |
| CN110299452A (en) * | 2019-06-28 | 2019-10-01 | 北京大学深圳研究生院 | A kind of perovskite UV photodetector and preparation method thereof |
| CN110931642A (en) * | 2019-11-29 | 2020-03-27 | 南昌大学 | Ultraviolet light detector of two-dimensional perovskite single crystal and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113346021A (en) * | 2021-04-12 | 2021-09-03 | 西安电子科技大学 | One kind contains (BA)2Cs5Pb6Cl19Visible light blind ultraviolet detector for perovskite layer and preparation method thereof |
| CN113809239A (en) * | 2021-08-25 | 2021-12-17 | 佛山仙湖实验室 | Perovskite thin film and anti-solvent preparation method of photoelectric detector containing perovskite thin film |
| CN113809239B (en) * | 2021-08-25 | 2024-03-05 | 佛山仙湖实验室 | Perovskite film and preparation method of anti-solvent of photoelectric detector containing perovskite film |
| CN114958336A (en) * | 2022-04-13 | 2022-08-30 | 香港理工大学深圳研究院 | Perovskite quantum dot, deep ultraviolet photoelectric detector and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112563420A (en) | Solar blind ultraviolet perovskite photoelectric detector and preparation method thereof | |
| US20080087326A1 (en) | Light-harvesting antennae for organic solar cells | |
| Sun et al. | Single-crystal perovskite detectors: development and perspectives | |
| CN109713128B (en) | Broadband near-infrared photoelectric detector and preparation method thereof | |
| CN110931642A (en) | Ultraviolet light detector of two-dimensional perovskite single crystal and preparation method thereof | |
| WO2017192022A1 (en) | Dye-sensitized solar cell comprising light collecting device panel | |
| CN108899421B (en) | All-inorganic perovskite solar cell and preparation method and application thereof | |
| CN103311439A (en) | Thin film photoconductive detector and manufacturing method and application thereof | |
| CN108376715B (en) | A kind of organic and inorganic charge-transfer complex infrared Absorption material and preparation method thereof | |
| CN110416333B (en) | Ultraviolet photoelectric detector and preparation method thereof | |
| CN113066931B (en) | spiro-MeOTAD/Ga 2 O 3 PerSi p-i-n type solar blind ultraviolet detector and preparation method thereof | |
| CN109449243A (en) | II type hetero-junctions near infrared photodetector and preparation method thereof based on two-dimentional molybdenum disulfide nano film and cadmium-telluride crystal | |
| CN104820006A (en) | Preparation method and application of photoelectrochemical sensor for sensitively detecting Cd<2+> based on ZnO and CdS compound semiconductor material | |
| CN115557709A (en) | Anti-reflection type light conversion glass film layer and preparation method thereof | |
| CN102891256B (en) | Cu(I) complex-based visible dead zone organic ultraviolet light detector | |
| TWI732704B (en) | Perovskite metal-semiconductor-metal photodetector and its manufacturing method | |
| KR102242331B1 (en) | Solar Cell Including a Transparent Electrode Containing a Phosphor and Method for Manufacturing the Same | |
| KR102531001B1 (en) | Perovskite Halide Thin Film That Receives Or Emits Blue Light And Manufacturing Method Thereof And Electronic Device Thereof | |
| CN111952383B (en) | CsPbBr3-CsPb2Br5Self-driven visible light photoelectric detector of all-inorganic mixed perovskite thin film | |
| Liu et al. | Luminescence enrichment in perovskite-lanthanide composites: Complexity and complementarity | |
| CN109346461B (en) | Photoelectric thermoelectric composite self-driven photoelectric detector and preparation method thereof | |
| CN109326587B (en) | Three-in-one composite self-driven photoelectric detector and preparation method thereof | |
| CN114242831A (en) | CdTe/CsPbBr3Preparation method of quantum dot heterojunction light detection film | |
| CN113451435A (en) | Single-crystal gallium oxide based solar blind ultraviolet photoelectric detector and preparation method and application thereof | |
| KR102442755B1 (en) | Solar energy converting materials and Solar cell comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210326 |