CN115124256B - Preparation method of all-inorganic perovskite film and narrow-band photoelectric detector - Google Patents
Preparation method of all-inorganic perovskite film and narrow-band photoelectric detector Download PDFInfo
- Publication number
- CN115124256B CN115124256B CN202210729797.3A CN202210729797A CN115124256B CN 115124256 B CN115124256 B CN 115124256B CN 202210729797 A CN202210729797 A CN 202210729797A CN 115124256 B CN115124256 B CN 115124256B
- Authority
- CN
- China
- Prior art keywords
- film
- cspbx
- perovskite
- solution
- heating
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 101
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 238000005507 spraying Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims description 182
- 239000000243 solution Substances 0.000 claims description 129
- 239000000758 substrate Substances 0.000 claims description 94
- 239000007787 solid Substances 0.000 claims description 61
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 58
- 238000001035 drying Methods 0.000 claims description 35
- 239000010409 thin film Substances 0.000 claims description 29
- 238000000889 atomisation Methods 0.000 claims description 25
- 230000005525 hole transport Effects 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- GVLGAFRNYJVHBC-UHFFFAOYSA-N hydrate;hydrobromide Chemical compound O.Br GVLGAFRNYJVHBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 32
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 229910052792 caesium Inorganic materials 0.000 abstract description 4
- -1 cesium halide Chemical class 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 150000004820 halides Chemical class 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- 239000007921 spray Substances 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 238000000151 deposition Methods 0.000 description 20
- 229910010413 TiO 2 Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 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 15
- 230000001276 controlling effect Effects 0.000 description 13
- 239000011261 inert gas Substances 0.000 description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- 239000004926 polymethyl methacrylate Substances 0.000 description 12
- 238000004528 spin coating Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 229910006404 SnO 2 Inorganic materials 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 8
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- DEUJSGDXBNTQMY-UHFFFAOYSA-N 1,2,2-trifluoroethanol Chemical compound OC(F)C(F)F DEUJSGDXBNTQMY-UHFFFAOYSA-N 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 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 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention provides a preparation method of an all-inorganic perovskite film and a narrow-band photoelectric detector. According to the preparation method, a certain amount of lead halide and cesium halide powder are respectively dissolved in different solvents to prepare perovskite powder, then the perovskite powder is dissolved in DMSO and DMF to obtain a perovskite precursor solution, an ALS spraying process is adopted to obtain a perovskite film, the quality of the film is optimized while the solubility of the perovskite is improved, and finally the obtained perovskite film is good in compactness, high in quality and high in crystallinity and is beneficial to charge transmission. According to the invention, after the perovskite film is obtained, the perovskite film is further subjected to high-temperature heating treatment, and for the film subjected to the heating treatment, crystal particles become larger and even can span the thickness of the whole film, all perovskite films show good continuity and flatness, the crystallization rate of the film is increased, the crystallization quality of the film is improved, defects in crystal lattices can be reduced, and the flatness of the film and the carrier transmission capability are optimized.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, relates to a photoelectric conversion technology, and in particular relates to a preparation method of an all-inorganic perovskite film and a narrow-band photoelectric detector.
Background
Photodetectors, also known as photosensors, may convert light signals into electrical signals. When the photoelectric material is irradiated with light, photon energy is equal to or greater than the band gap, a photo-generated carrier is generated to form an electric signal. Has great potential and wide application in the fields of spectrum, optical communication, environmental monitoring, biological detection and the like. Photodetectors can be classified into broadband photodetectors and narrowband photodetectors, depending on the size of the spectral response width. Broadband photodetectors are capable of detecting a relatively broad range of wavelengths within which a flat and high External Quantum Efficiency (EQE) spectrum is desired, primarily for polychromatic light detection and imaging. In contrast, narrow-band photodetectors, which have a small full width at half maximum (FWHM) and a high EQE value over a specific and relatively narrow wavelength range, are mainly used for optical detection of specific wavelengths, such as biological detection, intelligent monitoring and security systems.
In general, the spectral response of a photodetector depends on the light absorption of the active material and the charge collection characteristics of the device. The regulation and control of the light absorption of the photoelectric detector comprise a coupling optical bandpass filter, a plasma resonance, a coupling optical microcavity and the like; the charge collection characteristics may be achieved by increasing the thickness of the photoactive layer or introducing surface charge recombination to form a Charge Collection Narrowing (CCN) effect, etc. The photoactive layer of a photodetector is typically a semiconductor material, so the optical and electrical properties of the semiconductor are decisive for the performance of the photodetector.
In recent years, organic-inorganic hybrid perovskites have been known to have 10 in the ultraviolet-visible region due to their excellent photoelectric properties, such as high carrier mobility, high dielectric constant 5 cm -1 The high absorption coefficient and the high defect tolerance of the polymer are of great research interest in the field of photoelectric devices. Although organic-inorganic hybrid perovskites have relatively excellent properties, they have unavoidable disadvantages such as instability under light irradiation, easy decomposition, and also easy decomposition by moisture at ordinary temperature. In summary, light, oxygen, humidity, temperature, defects all affect the stability of the organic-inorganic hybrid perovskite in the device. Oxygen and moisture in the air are important causes of organic-inorganic hybrid perovskite decomposition. The effect of oxygen on the organic-inorganic hybrid perovskite may also be considered to be related to illumination. Because the ultraviolet rays in the sunlight can form super oxidation with oxygen Object O 2- The super oxide can react with A-site cations of the organic-inorganic hybrid perovskite, so that the structure of the perovskite is damaged, and the organic functional groups contained in the super oxide can lead the organic-inorganic hybrid perovskite photoelectric detector to have poor chemical property and thermal stability, so that the super oxide has certain limitation in the photoelectric research field.
By using inorganic cations Cs + This disadvantage can be compensated for. All-inorganic perovskite CsPbX 3 (x=cl, br, I) has a similar structure to that of the organic-inorganic hybrid perovskite, and has more excellent luminescence property, high fluorescence quantum yield (90%), better stability, narrow emission peak (half width Quan Feng-42 nm), emission spectrum covering the whole visible light range, and crystal phase changing with the difference of halogen elements contained in the synthesis temperature and its molecular formula. Due to CsPbX 3 Having the above excellent light emitting characteristics has attracted attention in the field of light emitting materials. The first all-inorganic perovskite photodetector was CsPbX reported by Lee et al 3 (x=cl, br, I) nanocrystals were prepared by simple, rapid, reproducible ion exchange reactions at room temperature and demonstrated broad band tuning (425-655 nm) and good on-off ratio (10 5 ). All inorganic perovskite CsPbBr has also been reported by sea wave et al 3 Compared with organic-inorganic hybrid perovskite, the organic-inorganic hybrid perovskite has more excellent stability, and the photocurrent of the organic-inorganic hybrid perovskite is hardly attenuated after long-time illumination. Meanwhile, it has been reported that CsPbBr is constructed using a flexible material as a substrate 3 The photodetector has very good stability and flexibility.
The optical and electrical properties of the all-inorganic perovskite photoelectric detector are affected by the surface morphology, which is directly related to photoelectric properties such as light absorption and carrier transport, and good surface morphology is a prerequisite for realizing high performance of the device. However, up to the present, the grain size of the film which can be grown is very small, so that the development and optimization of the preparation process of the perovskite film are necessary conditions for realizing successful application of the perovskite material as a photosensitive layer in the photovoltaic field, the luminous field, the laser field and the like. The existing method for preparing the all-inorganic perovskite thin film and the photoelectric detector mainly comprises the following steps:
1. solution process
The most commonly used process for preparing a thin film by a solution method is spin coating, and can be classified into one-step spin coating and two-step spin coating.
(1) The one-step spin coating method is to spin-coat the perovskite precursor solution prepared in advance on the prepared substrate material, and anneal the substrate material after spin coating is finished, so that a usable perovskite film is finally formed. When the perovskite film is prepared by adopting the one-step spin coating method, the quality of the finally formed perovskite film can be obviously influenced by the selected organic solvent and the annealing process, if the organic solvent is improperly selected, the finally prepared perovskite film can generate grain clusters, so that the film can not completely cover the substrate, and the problem of holes exists.
(2) The two-step spin coating method is also called a two-step sequential deposition method (CsPbX 3 For example), lead halide and cesium halide are first dissolved in different solvents, a layer of lead halide film is deposited by spin coating, then a layer of cesium halide film is deposited, the two films react with each other, and finally a perovskite film is formed. Finally, the perovskite film is annealed to obtain the desired crystalline phase. Compared with the one-step spin coating method, the perovskite film prepared by the two-step spin coating method improves the crystallization quality and the surface coverage rate of the film. However, the prepared film has a problem of poor reproducibility due to more parameters to be controlled in the process of preparing the film by the two-step spin coating method. In addition, the two films react with each other, and there may be a case where the precursor solution is excessively reacted or the reaction is not complete, affecting the quality of the finally formed perovskite film.
2. Vacuum process
Vacuum thermal evaporation is a well-established technique used in the field of coating, which allows easy deposition of multilayer thin films over large areas, and the deposited thin films have good uniformity and flatness. The vacuum thermal evaporation coating can accurately control the thickness of the film, and the repeatability of the film is high. However, the coating technology is complex to operate and has high cost.
3. Chemical Vapor Deposition (CVD) method
For preparing the all-inorganic perovskite film (CsPbX 3 For example), pbX can be used 2 And CsX, placing the deposited substrate in a low temperature region at the downstream, and controlling the deposition of perovskite on the substrate by adjusting the temperature, pressure, reaction time and the like. At present, all-inorganic perovskite thin films prepared by CVD are often prepared with small crystal sizes and cannot be used for constructing perovskite thin film devices, so that the growth conditions of perovskite thin film crystals with larger sizes need to be explored.
4. Spray coating process
The spray coating method is to atomize the perovskite solution by ultrasonic to form aerosol and deposit the aerosol on the preheated conductive substrate. However, the perovskite thin film prepared by the method has large surface roughness and is less used for preparing perovskite photodetectors.
In the preparation process of the all-inorganic perovskite film, the problems of incomplete coverage and non-compact holes in the film of the perovskite film prepared by the one-step spin coating method are solved by the method. However, they have disadvantages such as poor reproducibility of the film produced, small grain size of the film produced, rough surface, poor film quality, etc., and generally lower photodetection performance. Therefore, it is urgent to develop a simple low-temperature process for preparing high-quality all-inorganic perovskite thin film.
Disclosure of Invention
The invention aims to solve the problems existing in the prior art when perovskite films and detectors are prepared, and thus provides a preparation method of an all-inorganic perovskite film and an all-inorganic narrow-band photoelectric detector. The perovskite thin film prepared by the method has large grain size and high film forming quality, and the thickness of the thin film can be effectively regulated and controlled by controlling the deposition times, so that the narrow-band photoelectric detector has excellent performance.
In order to solve the technical problems, the invention is realized by the following technical scheme.
The first aspect of the invention provides a preparation method of an all-inorganic perovskite thin film, which comprises the following steps:
(1) PbX is processed 2 Dissolving in HBr water solution to form pale yellow solution; subsequently, csX aqueous solution was continuously added to obtain an orange solid; washing and suction filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) Drying CsPbX 3 Dissolving the powder in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and stirring to obtain CsPbX 3 A precursor solution;
(3) Carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) CsPbX obtained in the step (2) is processed 3 The precursor solution is subjected to ultrasonic atomization treatment and is uniformly sprayed on a transparent conductive substrate in a driving scanning mode to form CsPbX 3 Precursor liquid film, and uniform CsPbX is formed after solvent is volatilized 3 A solid film;
(5) CsPbX obtained in the step (4) is processed 3 The solid film is heat treated to promote further growth of the crystal.
Wherein, X is selected from one or more of Cl, br and I.
Preferably, the drying in step (1) is performed under vacuum, and the drying temperature is 60 ℃.
Preferably, the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide in the step (2) is 0.5-2:1.
Preferably, the ultrasonic cleaning in the step (3) is specifically: and sequentially carrying out ultrasonic cleaning on the transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol.
Preferably, the transparent conductive substrate in the step (3) is selected from one or more of FTO and ITO.
Preferably, the CsPbX in step (4) 3 The ultrasonic atomization treatment of the precursor solution specifically comprises the following steps: csPbX 3 The precursor solution is added into an atomization container, and the CsPbX is added under the action of an ultrasonic atomizer 3 The precursor solution is atomized.
As a preferenceSpecifically, the spraying in the step (4) is as follows: placing transparent conductive substrate on heating table, introducing inert gas into atomization container, and atomizing to obtain CsPbX 3 The precursor solution is evenly sprayed on the heated substrate through a spray head under the drive of the inert gas.
Preferably, the temperature of the heating table is 120-200 ℃.
Preferably, the flow rate of the inert gas is 1-3L/min; most preferably, the inert gas is selected from nitrogen.
Preferably, in the spraying process, the height of the spray head from the transparent conductive substrate is 1-10mm, the scanning speed is 0.2-2.5cm/s, and the scanning times are 2-32 times; csPbX can be controlled by setting the number of driving scans 3 Thickness of the solid film.
Preferably, the heating temperature in the step (5) is 300-400 ℃ and the heating time is 1-60min, so that the residual solvent in the perovskite solid film volatilizes, grains are promoted to further grow, and the crystallinity of the perovskite film is improved.
In a second aspect, the invention provides an all-inorganic perovskite thin film prepared according to the method.
The third aspect of the invention provides an all-inorganic perovskite narrow-band photodetector comprising, in order, a transparent conductive substrate layer, a hole transport layer, csPbX 3 A solid film layer, an electron transport layer and an electrode layer, wherein X is selected from one or more of Cl, br and I.
Preferably, the transparent conductive substrate is selected from one or more of FTO and ITO.
Preferably, the hole transport layer is selected from NiO y 。
Preferably, the electron transport layer is selected from TiO 2 、SnO 2 One or more of fullerene derivative PCBM; more preferably, the electron transport layer is selected from TiO 2 、SnO 2 One or more of the following; most preferably, the electron transport layer is selected from the group consisting of TiO 2 。
Preferably, the electrode layer is selected from silver.
The fourth aspect of the invention provides a method for preparing an all-inorganic perovskite narrow-band photoelectric detector, which comprises the following steps:
(1) PbX is processed 2 Dissolving in HBr water solution to form pale yellow solution; subsequently, csX aqueous solution was continuously added to obtain an orange solid; washing and suction filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) Drying CsPbX 3 Dissolving the powder in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and stirring to obtain CsPbX 3 A precursor solution;
(3) Carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) Uniformly spraying the hole transport layer solution on a dried substrate in a driving scanning mode after ultrasonic atomization treatment, and volatilizing a solvent to form a hole transport layer film;
(5) CsPbX obtained in the step (2) is processed 3 Performing ultrasonic atomization treatment on the precursor solution, and uniformly spraying the precursor solution on the hole transport layer film obtained in the step (4) in a driving scanning mode to form CsPbX 3 Precursor liquid film, and uniform CsPbX is formed after solvent is volatilized 3 A solid film;
(6) CsPbX obtained in step (5) 3 Heating the solid film to promote the further growth of the crystal;
(7) Carrying out ultrasonic atomization treatment on the electron transport solution, and uniformly spraying the electron transport solution on the CsPbX subjected to the heating treatment in the step (6) in a driving scanning mode 3 Forming an electron transport layer film on the surface of the solid film;
(8) Evaporating an electrode layer on the electron transport layer film to obtain the electron transport layer;
wherein, X is selected from one or more of Cl, br and I.
Preferably, the drying in step (1) is performed under vacuum, and the drying temperature is 60 ℃.
Preferably, the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide in the step (2) is 0.5-2:1.
Preferably, the ultrasonic cleaning in the step (3) is specifically: and sequentially carrying out ultrasonic cleaning on the transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol.
Preferably, the transparent conductive substrate in the step (3) is selected from one or more of FTO and ITO.
Preferably, the hole transport layer in step (4) is selected from NiO y The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the preparation method of the hole transport layer solution comprises the following steps: dissolving nickel acetylacetonate in acetonitrile solution to obtain the catalyst; most preferably, the NiO y The concentration of the solution is 0.008-0.02mol/L.
Preferably, the ultrasonic atomization treatment of the hole transport layer solution in the step (4) is specifically: and adding the hole transport layer solution into an atomization container, and atomizing the hole transport layer solution under the action of an ultrasonic atomizer.
Preferably, the spraying in the step (4) is specifically: heating the transparent conductive substrate, introducing mixed gas into an atomization container, and uniformly spraying atomized hole transport layer solution onto the heated substrate through a spray head under the drive of the mixed gas.
Preferably, the transparent substrate is heated at a temperature of 400-500 ℃.
Preferably, the flow rate of the inert gas is 1-3L/min; most preferably, the mixed gas is selected from air.
Preferably, in the spraying process, the height of the spray head from the transparent conductive substrate is 1-20mm, the scanning speed is 0.2-2cm/s, and the scanning times are 2-10 times; the thickness of the hole transport layer thin film can be controlled by setting the number of driving scans.
Further, after the spraying in the step (4), the hole transport layer film is optionally placed on a heating table at 400-500 ℃ for heating for 10-60min, and then naturally cooled to room temperature.
Preferably, the CsPbX in step (5) 3 Precursor(s)The ultrasonic atomization treatment of the bulk solution is specifically as follows: csPbX 3 The precursor solution is added into an atomization container, and the CsPbX is added under the action of an ultrasonic atomizer 3 The precursor solution is atomized.
Preferably, the spraying in the step (5) is specifically: heating the transparent conductive substrate sprayed with the hole transport layer film, introducing inert gas into an atomization container, and atomizing to obtain CsPbX 3 The precursor solution is evenly sprayed on the heated substrate through a spray head under the drive of the inert gas.
Preferably, the heating temperature of the transparent conductive substrate sprayed with the hole transport layer film is 120-200 ℃.
Preferably, the flow rate of the inert gas is 1-3L/min; most preferably, the inert gas is selected from nitrogen.
Preferably, in the spraying process, the height of the spray head from the transparent conductive substrate is 1-10mm, the scanning speed is 0.2-2.5cm/s, and the scanning times are 2-32 times; csPbX can be controlled by setting the number of driving scans 3 Thickness of the solid film.
Preferably, the heating temperature in the step (6) is 300-400 ℃ and the heating time is 1-60min.
Preferably, the electron transport layer is selected from TiO 2 、SnO 2 One or more of fullerene derivative PCBM; more preferably, the electron transport layer is selected from TiO 2 、SnO 2 One or more of the following; most preferably, the electron transport layer is selected from the group consisting of TiO 2 。
Preferably, the ultrasonic atomization treatment of the electron transport layer solution in the step (7) is specifically: the electron transport layer solution was added to an atomizing vessel and atomized by an ultrasonic atomizer.
Preferably, the spraying in the step (7) is specifically: spraying the step (6) with CsPbX 3 Heating the transparent conductive substrate of the solid film, introducing inert gas into an atomization container, and introducing atomized electron transport layer solution under the drive of the inert gas And uniformly spraying the heated substrate by a spray head.
Preferably, the spray is CsPbX 3 The transparent conductive substrate of the solid film is heated at 200-500 ℃.
Preferably, the flow rate of the inert gas is 1-3L/min; most preferably, the inert gas is selected from nitrogen.
Preferably, in the spraying process, the height of the spray head from the transparent conductive substrate is 5-20mm, the scanning speed is 0.1-3cm/s, and the scanning times are 1-8 times; the thickness of the electron transport layer film can be controlled by setting the number of driving scans.
Further, after the spraying in the step (7), the electron transport layer film is optionally placed on a heating table at 200-500 ℃ for heating for 30-120min, and then naturally cooled to room temperature.
Preferably, the electrode layer in step (8) is selected from silver.
Preferably, the electrode layer has a thickness of 80nm.
Compared with the prior art, the invention has the following technical effects:
(1) According to the invention, a certain amount of lead halide and cesium halide powder are respectively dissolved in different solvents to prepare perovskite powder, then the perovskite powder is dissolved in dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) to obtain a perovskite precursor solution, an ALS spraying process is adopted to obtain a perovskite film, and the direct dissolution of the perovskite raw material in the prior art can cause significant reduction of solubility, so that the quality of the sprayed film is poor. The method improves the solubility of the perovskite and optimizes the quality of the film, and the finally obtained perovskite film has the advantages of good compactness, high quality and high crystallinity, and is beneficial to charge transmission. In addition, the thickness of the perovskite film prepared by the method is controllable, the thickness of the film can be accurately regulated and controlled within 0.1-1000 mu m, and the condition of narrow-band detection is met.
(2) After the perovskite film is obtained, the perovskite film is further subjected to high-temperature heating treatment, and for the film subjected to the heating treatment, crystal particles become large and even can span the thickness of the whole film, and all perovskite films show good continuity and flatness. While the perovskite thin film crystal particles which are not subjected to the heat treatment are smaller, and some particles are piled up on other particles in the thin film growth direction. Therefore, the film is subjected to heating treatment, so that the crystallization rate of the film is increased, the crystallization quality of the film is improved, defects in crystal lattices can be reduced, and the flatness of the film and the carrier transmission capability are optimized.
(3) The all-inorganic perovskite photoelectric detector prepared by using the high-quality perovskite film has obvious narrow-band response at 535nm wavelength, the External Quantum Efficiency (EQE) of the detector is as high as 18%, and compared with a device using PCBM as an electron transmission layer, the detector has higher responsivity and detection rate and low noise; in addition, the stability of the all-inorganic perovskite photodetector is better.
Drawings
Fig. 1 is a schematic diagram of a perovskite thin film formation process provided by the present invention. Wherein a is the preparation of CsPbBr 3 Schematic representation of powder sample; b is a schematic diagram of perovskite film formation process.
FIG. 2 is CsPbBr prepared in example 2 3 SEM images and XRD images of the inorganic perovskite thin film, wherein a and c are front SEM images, b and d are cross-sectional SEM images, and (e) is an XRD image.
FIG. 3 is a graph of CsPbBr deposited at various thicknesses and heated for various times in example 2 3 Inorganic perovskite thin film SEM images, a, c, e, g, i, k are front SEM images, b, d, f, h, j, l are cross-sectional SEM images.
FIG. 4 is CsPbBr prepared in comparative example 1 3 SEM image of inorganic perovskite thin film.
FIG. 5 shows CsPbBr prepared in example 2 of the present invention 3 The inorganic perovskite photoelectric detector is structurally schematic.
FIG. 6 is CsPbBr prepared in example 2 of the present invention 3 Schematic of external quantum efficiency of inorganic perovskite photodetectors.
FIG. 7 shows CsPbBr prepared in example 2 of the present invention 3 Schematic of the responsivity of an inorganic perovskite photodetector.
FIG. 8 shows the present inventionCsPbBr prepared in EXAMPLE 2 3 The detection rate of the inorganic perovskite photoelectric detector.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the all-inorganic perovskite thin film comprises the following steps:
(1) 20mmol PbBr 2 Dissolved in 30ml of 48% aqueous HBr to form a pale yellow solution; subsequently, csBr in water (20 mmol CsBr in 10 ml water) was added continuously, immediately precipitating a bright orange solid; washing orange solid with absolute ethyl alcohol for multiple times, and suction filtering to obtain CsPbBr 3 Powder, followed by CsPbBr 3 Placing the powder into a vacuum drying oven at 60 ℃ for drying;
(2) 2.10g of dried CsPbBr was taken 3 Dissolving the powder in a mixed solvent of 14.5mL of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of DMSO to DMF is 2:1), and uniformly stirring to obtain CsPbBr 3 Precursor solution (molar concentration of 0.25 mol/L);
(3) Ultrasonic cleaning is carried out on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol in sequence, and then the FTO transparent conductive substrate is put into an oven for drying at 70 ℃ for standby;
(4) CsPbBr obtained in step (2) 3 Placing the precursor solution in an atomization container for ultrasonic atomization treatment, introducing dry nitrogen into the atomization container at a flow rate of 1.5L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle, and volatilizing the solvent at high temperature to form uniform CsPbBr 3 A solid film. In the process, the nozzle scans back and forth in the horizontal direction, and the CsPbBr is grown 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(5) After the scanning is completed, the obtained CsPbBr 3 Heating the solid film at 400 DEG COn the bench, different heating time is selected according to different film thickness, so that residual solvent in the perovskite solid film volatilizes, grains are promoted to further grow, and the crystallinity of the perovskite film is improved.
The all-inorganic perovskite film prepared by the method has higher density, larger grain size and more uniform surface. The process for forming the all-inorganic perovskite thin film is shown in FIG. 1, wherein FIG. 1 (a) is a process for preparing CsPbBr 3 Schematic representation of powder sample; FIG. 1 (b) is a schematic diagram of a perovskite thin film formation process.
Example 2
CsPbBr 3 The preparation method of the perovskite narrow-band photoelectric detector comprises the following steps:
(1) 20mmol PbBr 2 Dissolved in 30ml of 48% aqueous HBr to form a pale yellow solution; subsequently, csBr in water (20 mmol CsBr in 10 ml water) was added continuously, immediately precipitating a bright orange solid; washing orange solid with absolute ethyl alcohol for multiple times, and suction filtering to obtain CsPbBr 3 Powder, followed by CsPbBr 3 Placing the powder into a vacuum drying oven at 60 ℃ for drying;
(2) 2.10g of dried CsPbBr was taken 3 Dissolving the powder in a mixed solvent of 14.5mL of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of DMSO to DMF is 2:1), and uniformly stirring to obtain CsPbBr 3 Precursor solution (molar concentration of 0.25 mol/L);
(3) Ultrasonic cleaning is carried out on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol in sequence, and then the FTO transparent conductive substrate is put into an oven for drying at 70 ℃ for standby;
(4) Dissolving nickel acetylacetonate in acetonitrile solution, uniformly mixing the two solutions according to the ratio of 1:25 to obtain NiO y A solution; placing a transparent conductive substrate on a heating table, heating the heating table to 475 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 1cm, and controlling the moving speed of a nozzle to 1.6 cm/s; niO is treated by y Atomizing the solution to form atomized NiO y A solution; introducing mixed gas into an atomizing device at a flow rate of 2L/min to atomize liquid dropsEvenly spraying the mixture on a conductive substrate through a nozzle to form even NiO y A film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown NiO y The deposition was continued on the film, and the number of scans was 8. After the scanning is completed, the obtained NiO is processed y Placing the film on a heating table at 500 ℃ for 30min, and cooling to room temperature;
(5) Will be sprayed with NiO y Placing the conductive substrate of the film on a heating table, heating the heating table to 140 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 5mm, and controlling the moving speed of a nozzle to 1.6cm/s; csPbBr 3 Atomizing the precursor solution to form atomized CsPbBr 3 A precursor solution; dry nitrogen is selected to be introduced into an atomization device at a flow rate of 1.5L/min, so that atomized liquid drops are uniformly sprayed on a conductive substrate through a nozzle, and a solvent volatilizes at a high temperature to form uniform CsPbBr 3 A solid film. In the process, the nozzle scans back and forth in the horizontal direction, and the CsPbBr is grown 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(6) After the scanning is completed, the obtained CsPbBr 3 Placing the solid film on a heating table at 400 ℃, and selecting different heating time according to different film thickness;
(7) Dissolving titanium isopropoxide in isopropanol solution, and uniformly mixing the two solutions according to the ratio of 1:20 to obtain TiO 2 A solution; placing the deposited perovskite film on a heating table with the temperature of 400 ℃ for heating; the distance between the nozzle and the upper surface of the conductive substrate is regulated to be 2cm, and the moving speed of the nozzle is controlled to be 1.7cm/s; tiO is mixed with 2 Atomizing the solution to form atomized TiO 2 A solution; introducing dry oxygen into an atomizing device at a flow rate of 2.4L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniform TiO 2 A film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown TiO 2 The deposition was continued on the film, and the number of scans was 4. After the scanning is completed, the obtained TiO 2 Placing the film on a heating table at 400 ℃ for 120min, and naturally cooling to room temperature;
(8) In TiO 2 Evaporating Ag electrode with thickness of 80 nm on the film layer to obtain CsPbBr 3 A narrow band photodetector.
Example 3
CsPbCl 3 The preparation method of the perovskite narrow-band photoelectric detector comprises the following steps:
(1) 26mmol of PbCl 2 To this solution was added continuously aqueous CsCl (26 mmol CsCl in 10ml water) in 20ml 48% aqueous HBr, and the solid precipitated immediately; washing the solid sample with absolute ethyl alcohol for multiple times, and suction filtering to obtain CsPbCl 3 Powder, followed by CsPbCl 3 Placing the powder sample in a vacuum drying oven at 60 ℃ for drying;
(2) 1.62g CsPbCl was taken 3 Dissolving the powder in a mixed solvent of 18.1ml of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of DMSO to DMF is (0.5:1)), and stirring uniformly to obtain CsPbCl 3 Precursor solution (molar concentration of 0.2 mol/L);
(3) Ultrasonic cleaning is carried out on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol in sequence, and then the FTO transparent conductive substrate is put into an oven for drying at 70 ℃ for standby;
(4) Dissolving nickel acetylacetonate in acetonitrile solution, uniformly mixing the two solutions according to the ratio of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 500 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 9mm, and controlling the moving speed of a nozzle to be 1.8 cm/s; niO is treated by y Atomizing the solution to form atomized NiO y A solution; introducing dry nitrogen into an atomizing device at a flow rate of 3L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniform NiO y A solution film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown NiO y The deposition was continued on the solution film, and the number of scans was 8. After the scanning is completed, the obtained NiO is processed y Placing the solution film on a heating table at 450 ℃ for 30min, and cooling to room temperature;
(5) Will be sprayed with NiO y The conductive substrate of the film is arranged on a heating table for heatingThe temperature of the table is increased to 200 ℃, the distance between the nozzle and the upper surface of the conductive substrate is adjusted to 8mm, and the moving speed of the nozzle is controlled to be 2cm/s; csPbCl 3 Atomizing the precursor solution to form atomized CsPbCl 3 Introducing dry nitrogen gas into an atomizing device at a flow rate of 2.5L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle, and volatilizing the solvent at high temperature to form uniform CsPbCl 3 A solid film. In the process, the nozzle scans back and forth in the horizontal direction, and CsPbCl is grown 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(6) After the scanning is completed, the obtained CsPbCl 3 Placing the solid film on a 350 ℃ heating table, and selecting different heating time according to different film thickness;
(7) Dissolving titanium isopropoxide in isopropanol solution, and uniformly mixing the two solutions according to the ratio of 1:20 to obtain TiO 2 A solution; placing the deposited perovskite film on a heating table with the temperature of 400 ℃ for heating; the distance between the nozzle and the upper surface of the conductive substrate is regulated to be 2cm, and the moving speed of the nozzle is controlled to be 1.7cm/s; tiO is mixed with 2 Atomizing the solution to form atomized TiO 2 A solution; introducing dry nitrogen gas into an atomizing device at a flow rate of 2.4L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniform TiO 2 A film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown TiO 2 The deposition was continued on the film, and the number of scans was 4. After the scanning is completed, the obtained TiO 2 Placing the film on a heating table at 200 ℃ for 30min, and cooling to room temperature;
(8) Then at TiO 2 Evaporating Ag electrode with thickness of 80 nm on the film layer to obtain CsPbBr 3 A narrow band photodetector.
Example 4
CsPbI 3 The preparation method of the perovskite narrow-band photoelectric detector comprises the following steps:
(1) 16mmol PbI 2 Dissolved in 25ml of 48% aqueous HBr, to which was added continuously aqueous CsI (16 mmol CsI in 8ml water) Immediately precipitating a solid; washing and suction-filtering the sample solid for multiple times by using absolute ethyl alcohol to obtain CsPbI 3 Powder, followed by CsPbI 3 Placing the powder sample in a vacuum drying oven at 60 ℃ for drying;
(2) Will 2.61g CsPbI 3 Dissolving the powder in a mixed solvent of 12ml of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of DMSO to DMF is 1:1), and stirring uniformly to obtain CsPbI 3 Precursor solution (molar concentration of 0.3 mol/L);
(3) Ultrasonic cleaning is carried out on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol in sequence, and then the FTO transparent conductive substrate is put into an oven for drying at 70 ℃ for standby;
(4) Dissolving nickel acetylacetonate in acetonitrile solution, uniformly mixing the two solutions according to the ratio of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 450 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 8mm, and controlling the moving speed of a nozzle to 1.6 cm/s; niO is treated by y Atomizing the solution to form atomized NiO y A solution; introducing dry nitrogen gas into an atomizing device at a flow rate of 2.5L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniform NiO y A film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown NiO y The deposition was continued on the film, and the number of scans was 8. After the scanning is completed, the obtained NiO is processed y Placing the film on a heating table at 500 ℃ for 10min, and cooling to room temperature;
(5) Will be sprayed with NiO y Placing the conductive substrate of the film on a heating table, heating the heating table to 180 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 7mm, and controlling the moving speed of the nozzle to 1.8cm/s; csPbI 3 Atomizing the precursor solution to form atomized CsPbI 3 Introducing dry nitrogen gas into an atomizing device at a flow rate of 1.8L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle, and volatilizing the solvent at high temperature to form uniform CsPbI 3 A solid film. In the process, the nozzle scans back and forth in the horizontal direction, and Cs are grown PbI 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(6) After the scanning is completed, the obtained CsPbI 3 Placing the solid film on a heating table at 300 ℃, and selecting different heating time according to different film thickness;
(7) SnO is prepared 2 Dissolving the nano particles in an aqueous solution to obtain SnO 2 A solution; placing the deposited perovskite film on a heating table with the temperature of 350 ℃ for heating; the distance between the nozzle and the upper surface of the conductive substrate is regulated to be 1.5cm, and the moving speed of the nozzle is controlled to be 2cm/s; snO is prepared 2 Atomizing the solution to form atomized SnO 2 A solution; introducing dry nitrogen gas into an atomizing device at a flow rate of 2.6L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniform SnO 2 A film. In the process, the nozzle scans back and forth in the horizontal direction, and the growing SnO 2 Continuously depositing on the film, wherein the scanning times are 8 times; after the scanning is completed, the obtained SnO 2 Placing the film on a heating table at 500 ℃ for 50min, and cooling to room temperature;
(8) Subsequently at SnO 2 Evaporating Ag electrode with thickness of 80nm on the film layer to obtain CsPbBr 3 A narrow band photodetector.
Example 5
CsPbI 2 The preparation method of the Br perovskite narrow-band photoelectric detector comprises the following steps:
(1) 17.2mmol PbBr 2 17.2mmol CsBr was dissolved in 30ml 48% aqueous HBr, to which PbI was continuously added 2 And CsI aqueous solution (17.2 mmol PbI) 2 And CsI is dissolved in 20ml of water) to immediately precipitate solid, and the solid sample is subjected to repeated washing and suction filtration by using absolute ethyl alcohol to obtain CsPbI 2 Br powder, followed by CsPbI 2 Placing Br powder into a vacuum drying oven at 60 ℃ for drying;
(2) 2.44g CsPbI was taken 2 Br powder is dissolved in a mixed solvent of 14.5ml of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of DMSO to DMF is 2:1), and the mixture is stirred uniformly to obtain CsPbI 2 Br precursor solutionMolar concentration is 0.25 mol/L);
(3) Ultrasonic cleaning is carried out on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol in sequence, and then the FTO transparent conductive substrate is put into an oven for drying at 70 ℃ for standby;
(4) Dissolving nickel acetylacetonate in acetonitrile solution, uniformly mixing the two solutions according to the ratio of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 425 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 7mm, and controlling the moving speed of a nozzle to 1.6cm/s; niO is treated by y Atomizing the solution to form atomized NiO y A solution; introducing dry nitrogen gas into an atomizing device at a flow rate of 1.8L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniform NiO y A film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown NiO y The deposition was continued on the film, and the number of scans was 8. After the scanning is completed, the obtained NiO is processed y Placing the film on a heating table at 400 ℃ for 30min, and cooling to room temperature;
(5) Will be sprayed with NiO y Placing the conductive substrate of the film on a heating table, heating the heating table to 160 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 6mm, and controlling the moving speed of the nozzle to 1.6cm/s; csPbI 2 The Br precursor solution is atomized to form atomized CsPbI 2 Feeding dry nitrogen gas into an atomization device at a flow rate of 1.6L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle, and volatilizing a solvent at a high temperature to form uniform CsPbI 2 A solid film of Br. In the process, the nozzle scans back and forth in the horizontal direction, and the CsPbI is grown 2 Continuously depositing the Br solid film, wherein the scanning times are 2-32 times;
(6) After the scanning is completed, the obtained CsPbI 2 Placing the Br solid film on a 350 ℃ heating table, and selecting different heating time according to different film thickness;
(7) Dissolving 1mg of PMMA powder in 1mL of chlorobenzene to obtain a PMMA solution, and dissolving 20mg of PCBM powder in 1mL of chlorobenzene to obtain a PCBM solution; 1mg of amino-functionalized diimine Dissolving amine polymer (PPDIN 6) in 2, 2-Trifluoroethanol (TFE) to obtain PPDIN6 solution; 30 mu L of PMMA solution was taken in the prepared CsPbI 2 Rotating the Br solid film at 7000rpm for 15s, drying, then taking 30 mu L of PCBM solution to rotate at 3000rpm for 30s on the PMMA film layer, drying, and then taking 30 mu L of PPDIN6 solution to rotate at 3000rpm for 30s on the PCBM film layer;
(8) Evaporating an Ag electrode with the thickness of 80nm on the PPDIN6 film layer to finally obtain CsPbI 2 Br narrowband photodetector.
Example 6
CsPbBr 2 The preparation method of the Cl perovskite narrow-band photoelectric detector comprises the following steps:
(1) 5mmol PbBr 2 Dissolved in 40ml of 48% aqueous HBr, to which was continuously added aqueous CsCl (5 mmol CsCl in 15ml water) and immediately a solid precipitated; washing a solid sample with absolute ethyl alcohol for multiple times, and performing suction filtration to obtain CsPbBr 2 Cl powder, followed by CsPbBr 2 Placing the Cl powder into a vacuum drying oven at 60 ℃ for drying;
(2) Will 2.68g CsPbBr 2 Dissolving Cl powder in a mixed solvent of 14.5 ml dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of DMSO to DMF is 1:1), and uniformly stirring to obtain CsPbBr 2 Cl precursor solution (molar concentration 0.35 mol/L);
(3) Ultrasonic cleaning is carried out on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol in sequence, and then the FTO transparent conductive substrate is put into an oven for drying at 70 ℃ for standby;
(4) Dissolving nickel acetylacetonate in acetonitrile solution, uniformly mixing the two solutions according to the ratio of 1:25 to obtain NiO y A solution; placing a transparent conductive substrate on a heating table, heating the heating table to 400 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 6mm, and controlling the moving speed of a nozzle to be 1.4 cm/s; niO is treated by y Atomizing the solution to form atomized NiO y A solution; introducing dry nitrogen gas into an atomizing device at a flow rate of 1.6L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniformityNiO of (C) y A film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown NiO y The deposition was continued on the film, and the number of scans was 8. After the scanning is completed, the obtained NiO is processed y Placing the film on a heating table at 450 ℃ for 10min, and cooling to room temperature;
(5) Will be sprayed with NiO y Placing the conductive substrate of the film on a heating table, heating the heating table to 120 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 4mm, and controlling the moving speed of a nozzle to be 1.6cm/s; csPbBr 2 Atomizing the Cl precursor solution to form atomized CsPbBr 2 Introducing dry nitrogen gas into an atomizing device at a flow rate of 1.4L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle, and volatilizing a solvent at a high temperature to form uniform CsPbBr 2 A Cl solid film. In the process, the nozzle scans back and forth in the horizontal direction, and the CsPbBr is grown 2 Continuously depositing the Cl solid film, wherein the scanning times are 2-32 times;
(6) After the scanning is completed, the obtained CsPbBr 2 Placing the Cl solid film on a heating table at 400 ℃, and selecting different heating time according to different film thickness;
(7) Dissolving 1mg of PMMA powder in 1mL of chlorobenzene to obtain a PMMA solution, and dissolving 20mg of PCBM powder in 1mL of chlorobenzene to obtain a PCBM solution; 1mg of amino-functionalized diimine polymer (PPDI 6) was dissolved in 2, 2-Trifluoroethanol (TFE) to give a PPDI 6 solution; 30 mu L of PMMA solution was taken and prepared as CsPbBr 2 Rotating the Cl solid film at 7000rpm for 15s, drying, then taking 30 mu L of PCBM solution to rotate at 3000rpm for 30s on the PMMA film layer, drying, and then taking 30 mu L of PPDIN6 solution to rotate at 3000rpm for 30s on the PCBM film layer;
(8) Evaporating an Ag electrode with the thickness of 80nm on the PPDIN6 film layer to finally obtain CsPbBr 2 Cl narrow-band photodetectors.
The above experimental examples can also be exemplified by, for example, further changing N 2 The flow rate, the scanning speed, the distance between the nozzle and the substrate, the temperature of the hot stage, etc. can be properly obtained within the scope of the present inventionBut in order to further simplify the process, the parameters of the first and second embodiments are optimally selected.
Comparative example 1
Comparative example CsPbBr was prepared by direct dissolution 3 Inorganic perovskite thin film and CsPbBr prepared in example 3 The microscopic morphologies of the inorganic perovskite thin films were compared and characterized by SEM.
CsPbBr 3 The preparation method of the inorganic perovskite narrow-band photoelectric detector comprises the following steps:
(1) 1mmol PbBr 2 1 mmole of CsBr powder is dissolved in 12.5ml of mixed solvent of DMSO and DMF (the volume ratio of DMSO to DMF is 1:1), and the mixture is stirred uniformly to obtain CsPbBr 3 (molar concentration of 0.08 mol/L);
(2) Sequentially ultrasonically cleaning a transparent conductive substrate (such as FTO) by using deionized water, acetone, isopropanol and ethanol, and then drying in an oven at 70 ℃ for later use;
(3) NiO is treated by y The solution and acetonitrile solution are uniformly mixed according to the proportion of 1:25 to obtain NiO y A solution; placing a transparent conductive substrate on a heating table, heating the heating table to 475 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 5mm, and controlling the moving speed of a nozzle to 1.6cm/s; niO is treated by y Atomizing the solution to form atomized NiO y A solution; introducing dry nitrogen gas into an atomizing device at a flow rate of 1.6L/min to uniformly spray atomized liquid drops on a conductive substrate through a nozzle to form uniform NiO y A film. In the process, the nozzle scans back and forth in the horizontal direction, and the grown NiO y The deposition was continued on the film, and the number of scans was 8. After the scanning is completed, the obtained NiO is processed y Placing the film on a heating table at 500 ℃ for 30min, and cooling to room temperature;
(4) Will be sprayed with NiO y Placing the conductive substrate of the film on a heating table, heating the heating table to 140 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to 5mm, and controlling the moving speed of the nozzle to 1cm/s; csPbBr 3 Atomizing the precursor solution to form atomized CsPbBr 3 A precursor solution; dry nitrogen is selected to be introduced into an atomization device at a flow rate of 1.5L/min, so that atomized liquid drops are uniformly sprayed on a conductive substrate through a nozzle, and a solvent volatilizes at a high temperature to form uniform CsPbBr 3 A solid film. In the process, the nozzle scans back and forth in the horizontal direction, and the CsPbBr is grown 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(5) After the scanning is completed, the obtained CsPbBr 3 Placing the solid film on a 220 ℃ heating table and keeping for 10 min;
(6) Dissolving 1mg of PMMA powder in 1mL of chlorobenzene to obtain a PMMA solution, and dissolving 20mg of PCBM powder in 1mL of chlorobenzene to obtain a PCBM solution; 1mg of amino-functionalized diimine polymer (PPDI 6) was dissolved in 2, 2-Trifluoroethanol (TFE) to give a PPDI 6 solution; 30 mu L of PMMA solution was taken and prepared as CsPbBr 3 Rotating the solid film at 7000rpm for 15s, drying, then taking 30 mu L of PCBM solution to rotate at 3000rpm for 30s on the PMMA film layer, drying, and then taking 30 mu L of PPDIN6 solution to rotate at 3000rpm for 30s on the PCBM film layer;
(7) Evaporating an Ag electrode with the thickness of 80nm on the PPDIN6 film layer to finally obtain CsPbBr 3 A narrow band photodetector.
Verification example 1
CsPbBr obtained by example 2 3 The microstructure of the inorganic perovskite film was observed by a scanning electron microscope and an X-ray diffractometer, and the result is shown in fig. 2. Wherein FIGS. 2 a-2 c show CsPbBr deposited at 140 DEG C 3 Heating perovskite thin films on a heating table for 0min and 10min respectively, wherein the model of an instrument is JEOL JSM-7800F; as can be seen from FIG. 2a (heating for 0 min) and FIG. 2c (heating for 10 min), csPbBr was obtained after heating the perovskite thin film for 10min in the present example 3 The film surface is even and smooth, and the grain size is large. Fig. 2b (heating for 0 min) and fig. 2d show that the film thickness can reach several micrometers, in close contact with the substrate.
The crystal structure of the film was characterized by X-ray diffraction pattern, instrument model Bruker D8 Advance, as shown in figure 2e,CsPbBr prepared 3 The impurity peak appears after the film is heated for 0min, and impure CsPbBr is obtained 3 After the film is heated for 10min, the impurity peak disappears to obtain purer CsPbBr 3 A film. The presence of a plurality of diffraction peaks at 2 theta values, corresponding to the (100), (110), (200), (210), (211), (202) crystal planes of the CsPbBr3 monoclinic structure, respectively, indicates that the crystal structure of the obtained film is indeed CsPbBr 3 。
The film morphology obtained in example 2 with different times of scanning and spraying and different times of heating was then examined, and the results are shown in fig. 3. The results show that CsPbBr with increasing spraying times 3 The thickness of the film is increased from 1 micron to 6 microns, and the grain size of the film gradually becomes larger along with the extension of the heating time, which shows that the method can prepare the perovskite film with thicker grain size and higher quality. CsPbBr prepared by the method 3 The thickness of the inorganic perovskite film is controllable, so that the conditions for preparing the narrow-band photoelectric detector are met.
Further, csPbBr prepared by direct dissolution method in comparative example 1 was taken 3 The micro morphology of the inorganic perovskite thin film is detected, and the result is shown in fig. 4. It can be seen that CsPbBr is obtained by direct dissolution 3 The film is very uneven, and the grain size is far smaller than that of the perovskite film prepared by the method.
Verification example 2
In order to characterize the superiority of the narrow-band photodetector prepared by the method of the present invention, performance parameters such as apparent quantum efficiency (EQE), responsivity (R) and detection rate (D) were tested, wherein FIGS. 5-8 are CsPbBr prepared in example 2 of the present invention 3 Device structure and performance characterization of narrow-band photodetectors. As shown in FIG. 5, niO y CsPbBr as hole transport layer 3 Is a photoactive layer for absorbing photons; tiO (titanium dioxide) 2 As an electron transport layer:
the apparent quantum efficiency (EQE) of the photodetector is calculated as:
wherein the method comprises the steps ofJ ph For the photocurrent density,L ligh for the intensity of the incident light to be high,his a constant of planck, which is set to be the planck's constant,cin order to achieve the light velocity, the light beam is,λas a function of the wavelength(s),qis an electron charge.
Responsivity (R): is defined as the ratio of photocurrent to light intensity, and the formula is:
since responsivity is proportional to apparent quantum efficiency, responsivity can also be expressed as:
detection rate (D): the ability of the reaction device to detect weak light is related to the responsivity and noise of the detector as follows:
wherein,Ais the effective area of the photodetector and,Δfis the bandwidth of the electrons and,i n is the noise current. Noise is mainly caused by three sources: shot noise generated by dark current, johnson noise, and "flash" noise generated by thermal fluctuations. If the detector noise is dominated by shot noise, then the detection rate (D) can be expressed as:
wherein,J d is the dark current density.
FIG. 6 shows CsPbBr 3 Apparent quantum efficiency (EQE) of narrow-band photodetectorThe test results of (2) are shown in FIG. 7 for the responsivity of the detector and FIG. 8 for the detection rate of the detector.
The above detailed description describes the analysis method according to the present invention. It should be noted that the above description is only intended to help those skilled in the art to better understand the method and idea of the present invention, and is not intended to limit the related content. Those skilled in the art may make appropriate adjustments or modifications to the present invention without departing from the principle of the present invention, and such adjustments and modifications should also fall within the scope of the present invention.
Claims (5)
1. The preparation method of the all-inorganic perovskite film is characterized by comprising the following steps of:
(1) PbX is processed 2 Dissolving in HBr water solution to form pale yellow solution; subsequently, csX aqueous solution was continuously added to obtain an orange solid; washing and suction filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) Drying CsPbX 3 Dissolving the powder in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and stirring to obtain CsPbX 3 A precursor solution;
(3) Carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) CsPbX obtained in the step (2) is processed 3 The precursor solution is subjected to ultrasonic atomization treatment and is uniformly sprayed on a transparent conductive substrate in a driving scanning mode to form CsPbX 3 Precursor liquid film, and uniform CsPbX is formed after solvent is volatilized 3 A solid film;
(5) CsPbX obtained in the step (4) is processed 3 Heating the solid film to promote the further growth of the crystal; the heating temperature is 300-400 ℃, and the heating time is 1-60min;
wherein, X is selected from one or more of Cl, br and I.
2. The all-inorganic perovskite thin film prepared by the preparation method according to claim 1.
3. The preparation method of the all-inorganic perovskite narrow-band photoelectric detector is characterized by comprising the following steps of:
(1) PbX is processed 2 Dissolving in HBr water solution to form pale yellow solution; subsequently, csX aqueous solution was continuously added to obtain an orange solid; washing and suction filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) Drying CsPbX 3 Dissolving the powder in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and stirring to obtain CsPbX 3 A precursor solution;
(3) Carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) Uniformly spraying the hole transport layer solution on a dried substrate in a driving scanning mode after ultrasonic atomization treatment, and volatilizing a solvent to form a hole transport layer film;
(5) CsPbX obtained in the step (2) is processed 3 Performing ultrasonic atomization treatment on the precursor solution, and uniformly spraying the precursor solution on the hole transport layer film obtained in the step (4) in a driving scanning mode to form CsPbX 3 Precursor liquid film, and uniform CsPbX is formed after solvent is volatilized 3 A solid film;
(6) CsPbX obtained in step (5) 3 Heating the solid film to promote the further growth of the crystal; the heating temperature is 300-400 ℃, and the heating time is 1-60min;
(7) Carrying out ultrasonic atomization treatment on the electron transport solution, and uniformly spraying the electron transport solution on the CsPbX subjected to the heating treatment in the step (6) in a driving scanning mode 3 Forming an electron transport layer film on the surface of the solid film;
(8) Evaporating an electrode layer on the electron transport layer film to obtain the electron transport layer;
wherein, X is selected from one or more of Cl, br and I.
4. The method of claim 3, wherein after the spraying in the step (4), the hole transport layer film is optionally heated on a heating table at 400-500 ℃ for 10-60min and then naturally cooled to room temperature.
5. A method according to claim 3, wherein after the spraying in step (7) is completed, the electron transport layer film is optionally placed on a heating table at 200-500 ℃ and heated for 30-120min, and then naturally cooled to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210729797.3A CN115124256B (en) | 2022-06-24 | 2022-06-24 | Preparation method of all-inorganic perovskite film and narrow-band photoelectric detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210729797.3A CN115124256B (en) | 2022-06-24 | 2022-06-24 | Preparation method of all-inorganic perovskite film and narrow-band photoelectric detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115124256A CN115124256A (en) | 2022-09-30 |
| CN115124256B true CN115124256B (en) | 2024-02-20 |
Family
ID=83381029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210729797.3A Active CN115124256B (en) | 2022-06-24 | 2022-06-24 | Preparation method of all-inorganic perovskite film and narrow-band photoelectric detector |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115124256B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221612A (en) * | 2017-06-15 | 2017-09-29 | 西南大学 | A kind of preparation method of full-inorganic perovskite thin film |
| CN107603614A (en) * | 2017-09-12 | 2018-01-19 | 华中科技大学 | A kind of preparation method of metal halide perovskite quantum dot |
| CN108075020A (en) * | 2017-12-27 | 2018-05-25 | 中国科学院长春光学精密机械与物理研究所 | A kind of caesium lead halogen perovskite thin film material and a kind of light emitting diode and preparation method thereof |
| CN110886017A (en) * | 2019-11-29 | 2020-03-17 | 上海应用技术大学 | Preparation method of all-inorganic cesium-lead halogen perovskite nanocrystalline film |
| CN113637471A (en) * | 2021-08-31 | 2021-11-12 | 中山大学 | In-situ lead salt coated all-inorganic lead halide perovskite nanocrystalline fluorescent powder and preparation method and application thereof |
| CN113809190A (en) * | 2021-09-14 | 2021-12-17 | 中山大学 | Low-temperature preparation method and application of all-inorganic perovskite thin film |
| CN114235771A (en) * | 2021-12-23 | 2022-03-25 | 重庆大学 | Sensing detection method for heavy metal mercury ion detection |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201811537D0 (en) * | 2018-07-13 | 2018-08-29 | Univ Oxford Innovation Ltd | Turnable blue emitting lead halide perovskites |
-
2022
- 2022-06-24 CN CN202210729797.3A patent/CN115124256B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221612A (en) * | 2017-06-15 | 2017-09-29 | 西南大学 | A kind of preparation method of full-inorganic perovskite thin film |
| CN107603614A (en) * | 2017-09-12 | 2018-01-19 | 华中科技大学 | A kind of preparation method of metal halide perovskite quantum dot |
| CN108075020A (en) * | 2017-12-27 | 2018-05-25 | 中国科学院长春光学精密机械与物理研究所 | A kind of caesium lead halogen perovskite thin film material and a kind of light emitting diode and preparation method thereof |
| CN110886017A (en) * | 2019-11-29 | 2020-03-17 | 上海应用技术大学 | Preparation method of all-inorganic cesium-lead halogen perovskite nanocrystalline film |
| CN113637471A (en) * | 2021-08-31 | 2021-11-12 | 中山大学 | In-situ lead salt coated all-inorganic lead halide perovskite nanocrystalline fluorescent powder and preparation method and application thereof |
| CN113809190A (en) * | 2021-09-14 | 2021-12-17 | 中山大学 | Low-temperature preparation method and application of all-inorganic perovskite thin film |
| CN114235771A (en) * | 2021-12-23 | 2022-03-25 | 重庆大学 | Sensing detection method for heavy metal mercury ion detection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115124256A (en) | 2022-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hanna et al. | Low temperature-processed ZnO thin films for p–n junction-based visible-blind ultraviolet photodetectors | |
| Kumar et al. | Synthesis and characterization of nano zinc oxide by sol gel spin coating | |
| Alsultany et al. | Effects of ZnO seed layer thickness on catalyst-free growth of ZnO nanostructures for enhanced UV photoresponse | |
| CN109713058A (en) | The gallium oxide ultraviolet detector and its preparation method and application of surface phasmon enhancing | |
| CN107170896B (en) | Perovskite flexible photodetector and preparation method thereof | |
| CN113782681A (en) | ZnO quantum dot ultraviolet photoelectric detector mixed with MXene nano material and preparation method thereof | |
| CN108511607B (en) | TiO2Preparation method of cookie-shaped microspheres and method for preparing perovskite solar cell | |
| CN112582554A (en) | Perovskite double-band photoelectric detector and preparation method thereof | |
| Rakhra et al. | Structural, morphological, optical, electrical and agricultural properties of solvent/ZnO nanoparticles in the photodegradation of DR-23 dye | |
| KR101236969B1 (en) | Method of preparing titania nano-powder for dye-sensitized solar cell, method of preparing titania nano-dispersion, and photocatalyst | |
| CN111180596A (en) | Preparation method of perovskite thin film and narrow-band photoelectric detector | |
| Maleki et al. | The effect of antisolvent dropping delay time on the morphology and structure of the perovskite layer in the hole transport material free perovskite solar cells | |
| CN113437223A (en) | Double-layer perovskite thin film and preparation method and application thereof | |
| Srivathsa et al. | Ultraviolet photoconductivity and photoluminescence properties of spray pyrolyzed ZnO nanostructure: Effect of deposition temperature | |
| CN115124256B (en) | Preparation method of all-inorganic perovskite film and narrow-band photoelectric detector | |
| Rahman et al. | Impact of localized surface plasmon resonance on efficiency of zinc oxide nanowire-based organic–inorganic perovskite solar cells fabricated under ambient conditions | |
| Pîslaru-Dănescu et al. | Synthesis and characterization of antireflective ZnO nanoparticles coatings used for energy improving efficiency of silicone solar cells | |
| Chaudhary et al. | Evolution in surface coverage of CH 3 NH 3 PbI 3− X Cl X via heat assisted solvent vapour treatment and their effects on photovoltaic performance of devices | |
| Shariffudin et al. | Influence of drying temperature on the structural, optical, and electrical properties of layer-by-layer ZnO nanoparticles seeded catalyst | |
| CN108373483B (en) | Tin-based perovskite, preparation method thereof and solar cell | |
| CN110010770A (en) | A kind of preparation of the perovskite solar battery of gold bipyramid plasma enhancing | |
| CN114685555A (en) | Two dimension (PEA)2PbX4Nanosheet, preparation method and application of nanosheet in ultraviolet light detector | |
| CN113278419B (en) | perovskite-PbS quantum dot polycrystalline film, preparation method and application thereof, and near-infrared light detector | |
| Guo et al. | Postripening Fabrication and Self‐Driven Narrowband Photoresponse of Large‐Grain, Phase‐Pure CsPbBr3 Films | |
| Kaneva et al. | ZnO thin films preparation on glass substrates by two different sol-gel methods |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |