CN115148904B - Transparent and stable all-inorganic metal halogen perovskite photoelectric detector and preparation method and application thereof - Google Patents
Transparent and stable all-inorganic metal halogen perovskite photoelectric detector and preparation method and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 10
- 150000002367 halogens Chemical class 0.000 title claims abstract description 10
- 239000010408 film Substances 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 12
- 238000004528 spin coating Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 12
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- -1 cesium halide Chemical class 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical group [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229960000344 thiamine hydrochloride Drugs 0.000 abstract description 10
- 235000019190 thiamine hydrochloride Nutrition 0.000 abstract description 10
- 239000011747 thiamine hydrochloride Substances 0.000 abstract description 10
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 abstract description 10
- 230000004044 response Effects 0.000 abstract description 8
- 230000003595 spectral effect Effects 0.000 abstract description 7
- YJUMYFAHFVTFKQ-UHFFFAOYSA-N [Br].[I].[Pb].[Cs] Chemical compound [Br].[I].[Pb].[Cs] YJUMYFAHFVTFKQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000547 conjugated polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000011895 specific detection Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 description 1
- LNDFVHXALNWEMX-UHFFFAOYSA-L [Pb](I)I.[Cs] Chemical compound [Pb](I)I.[Cs] LNDFVHXALNWEMX-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TUJWIYZCAPMHSA-UHFFFAOYSA-N dipentylphosphoryloxybenzene Chemical compound CCCCCP(=O)(CCCCC)OC1=CC=CC=C1 TUJWIYZCAPMHSA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 235000019192 riboflavin Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K30/80—Constructional details
- H10K30/81—Electrodes
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H—ELECTRICITY
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Abstract
The invention provides a transparent stable high-performance all-inorganic metal halogen perovskite photoelectric detector element, and a preparation method and application thereof. The preparation process comprises the following steps: forming an electron transport layer film on the surface of the conductive substrate; inorganic perovskite material cesium lead iodine bromine (CsPbI) added with thiamine hydrochloride x Br y X+y=3) spin-coating on the electron transport layer film; the perovskite thin film prepared above is sequentially prepared into an organic conjugated polymer material and a metal electrode layer. The preparation process is simple, the spectral response range is wide, the transparency is high, and meanwhile, the prepared photoelectric detector has self-driving property, is convenient to miniaturize and portable, and has great potential application value.
Description
Technical Field
The invention belongs to the technical field of photoelectric detectors, and particularly relates to a transparent and stable all-inorganic metal halogen perovskite photoelectric detector element, and a preparation method and application thereof.
Background
Transparent/translucent photodetectors can be used to detect the optical signal and ensure that light passes through the device, an indispensable component in the next generation of optoelectronic devices. In recent years, inorganic perovskite CsPbX 3 (x=cl, br, I) has been widely studied in various applications due to its attractive optoelectronic properties and higher thermal stability compared to organic-inorganic hybrid perovskites. In particular CsPbI x Br y It balances spectral response range and phase stability and is further considered a promising candidate for high performance semitransparent ultraviolet-visible (UV-Vis) photodetectors. However, the purpose isCsPbI-based in the majority of previous reports x Br y The following problems are faced with the devices of: 1. because of poor humidity stability, the material still needs to be stored in a glove box or relatively low humidity<40%) in an air environment. For the problem of humidity stability, strategies such as crystal crosslinking, surface coverage or ion doping are adopted at present to improve CsPbI x Br y Is stable. Previous studies have shown that organic molecules containing amino or c=n groups can coordinate with the constituents of the perovskite, thereby controlling the growth of perovskite crystals or anchoring the perovskite, facilitating the stability of the film. 2. Most cannot be used to detect the wider infrared (NIR) region or to maintain transparency. For the problem of broad spectral response, materials that can combine light in the light response range are currently available. However, the above improvements are limited, and in order to obtain high performance devices with promising practical application, there is an urgent need to further design and construct stable transparent self-powered broad spectral response CsPbI x Br y Photodetectors are very important.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a transparent, stable and high-performance all-inorganic metal halogen perovskite photoelectric detector element, and a preparation method and application thereof. The preparation process is simple, the spectral response range is wide, the transparency is high, and meanwhile, the prepared photoelectric detector has self-driving property, is convenient to miniaturize and portable, and has great potential application value.
A first object of the present invention is to provide a method for preparing a transparent stable high performance all-inorganic metal halide perovskite photodetector element, comprising the steps of:
(1) Forming an electron transport layer on the surface of the conductive substrate;
(2) Adding lead halide, cesium halide and additives into organic solvent to obtain CsPbI x Br y The precursor solution is used for preparing the precursor solution,wherein x+y=3;
(3) CsPbI obtained in the step (2) is processed x Br y Spin-coating the precursor solution on the surface of the electron transport layer prepared in the step (1), and heating to obtain CsPbI x Br y A thin film layer;
(4) Dissolving polythiophene-pyrrolopyrrole dione (PDPP 3T) in a benzene solvent to obtain a polythiophene-pyrrolopyrrole dione precursor solution, and spin-coating the obtained PDPP3T precursor solution on CsPbI obtained in the step (3) x Br y The surface of the film layer;
(5) CsPbI obtained in step (4) x Br y And evaporating a metal electrode on the surface of the film layer to obtain the all-inorganic metal halogen perovskite photoelectric detector element.
In one embodiment of the present invention, in step (1), the conductive substrate is selected from Indium Tin Oxide (ITO) or fluorine doped tin oxide (FTO) conductive glass.
In one embodiment of the present invention, in step (1), the electron transport layer material is selected from one or more of tin oxide, titanium oxide, and zinc oxide.
In one embodiment of the invention, in step (2), the organic solvent is selected from DMSO and/or DMF; DMSO to DMF volume ratio of 1:99-99:1.
in one embodiment of the invention, in step (2), the additive is selected from the group consisting of a bis-NH containing 3 + Or NH + Organic compounds of cationic groups.
In one embodiment of the invention, the additive is selected from thiamine hydrochloride, riboflavin, nicotinamide, and the like.
In one embodiment of the invention, in step (2), the halogen in the lead halide or cesium halide is selected from chlorine, bromine or iodine.
In one embodiment of the invention, in step (2), the lead halide is selected from lead iodide or/and lead bromide; the cesium halide is selected from cesium iodide or/and cesium bromide.
In one embodiment of the present invention, in the step (2), the molar ratio of the lead halide to the cesium halide is 1:1.
In one embodiment of the invention, in the step (2), the concentration of the lead halide and the cesium halide in the organic solvent is 0.1-0.6mol/L.
In one embodiment of the present invention, in step (4), the benzene-based solvent is selected from one or more of chlorobenzene, phenetole, and toluene.
In one embodiment of the present invention, in step (4), the concentration of the PDPP3T in the benzene-based solvent is 0.1-7mg/mL.
In one embodiment of the invention, in step (5), the metal in the metal electrode is selected from gold, silver or copper.
A second object of the present invention is to provide an all-inorganic metal halide perovskite photodetector element obtained by the preparation method.
A third object of the present invention is the use of said all-inorganic metal halide perovskite photodetector element in the preparation of a photodetector.
It was found that control of crystal plane exposure is critical for inorganic perovskite optoelectronic devices. Films with different exposed crystal planes may exhibit different physical properties (photoelectric characteristics, conductivity, etc.) and chemical properties (stability, etc.) due to the anisotropy of crystals and different surface defect densities, thereby affecting the performance of the film. Theoretical calculations show that the band edge of the (110) plane is always lower than the energy of the (100) plane and thus in principle the electron-hole separation can be enhanced. In addition, the (110) face-exposed inorganic perovskite may also remain ultrastable in experimental studies due to the effect of electronic passivation of anionic ligands or grain size reduction.
Compared with the prior art, the technical scheme of the invention has the following advantages:
first, the invention successfully regulates the exposed crystal face of the perovskite film, thereby obtaining a high-quality film with high stability. This is mainly due to the NH of thiamine hydrochloride 3 + Or NH + The cationic groups perform a function similar to that of the methylammonium cation. Such organic biscationic structures can result in the formation of (110) -oriented perovskite.
Second, the improvement in film quality of the present invention brings about photoelectricityPerformance is improved, and the responsivity of the self-powered light source is still as high as 0.3A W under the light with the wavelength of 300-950nm -1 The specific detection rate reaches 10 13 Jones。
Third, the devices produced by the method of the present invention have higher transparency than conventional broad spectrum self-powered perovskite thin film devices.
The method provided by the invention has the advantages of simple preparation process, wide spectral response range and high transparency, and the prepared photoelectric detector has self-driving property, is convenient to miniaturize and portable, and has great potential application value.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings, in which
FIG. 1 is a SEM (scanning electron microscope) image of a perovskite prepared according to comparative example of the present invention;
FIG. 2 is a SEM (scanning Electron microscope) image of a perovskite prepared according to one embodiment of the invention;
FIG. 3 is a graph showing the responsivity and specific detection rate of photodetectors prepared in examples and comparative examples of the present invention at different optical wavelength bands;
FIG. 4 is a graph showing the transparency of a photodetector fabricated according to an embodiment of the present invention;
FIG. 5 is a photograph showing perovskite thin films of the present invention prepared in example one, example two, example three and comparative example one after being left for 1 day and 10 days under high humidity (60-70%); drawing a shows the film just prepared, drawing b shows the film after 1 day of standing, and drawing c shows the photograph after 10 days;
fig. 6 is an XRD pattern of perovskite prepared in example one and example two, example three and comparative example one.
FIG. 7 is an absorption diagram of perovskite prepared in example one and example two, example three and comparative example one; the a diagram is CsPbI 2 Br, b diagram CsPbI 2 Br-1, c is CsPbI 2 Br-5; d is CsPbI 2 Br-10。
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The invention introduces the thiamine hydrochloride to lead CsPbI 2 The main exposed crystal face of the Br perovskite is adjusted from the (200) face to the (110) face, and simultaneously, the organic conjugated polymer with a narrow band gap is further spin-coated on the perovskite, so that the spectral response range of the perovskite is widened, and the self-driving property is provided. On the basis, the transparent stable high-performance all-inorganic metal halogen perovskite photoelectric detector is constructed. The specific method is that firstly, an n-type semiconductor film is formed on conductive glass, and the residual solvent is removed by drying. Then forming CsPbI with different crystal face exposure on the n-type semiconductor film 2 Br perovskite thin film. Finally, PDPP3T is used as a spectrum widening material and a hole transport material is covered on CsPbI 2 And Br film. In the invention, the prepared photoelectric detector can be directly used for detecting elements, and in the following embodiments, the photoelectric detector prepared by the invention is directly used as an element to test the detection performance.
Example 1
(1) Drying the ITO conductive glass with the thickness of 1.5cm and 2cm after ultrasonic cleaning, carrying out ultraviolet ozone treatment for 10min, and then carrying out 50 mu L SnO 2 The precursor solution is spin-coated on the ITO conductive glass, the spin-coating speed is 5000 revolutions per minute, the acceleration is 1000 revolutions per second, and the spin-coating time is 30s. After spin coating is completed, the substrate is placed on a heating table at 60 ℃ and heated for 30min to remove residual solvent, and SnO is obtained 2 Film samples.
(2) 0.095g cesium bromide, 0.184g lead iodide, 5mg thiamine hydrochloride were added to 1mL DMSO and stirred at 70℃for 4 hours to give a yellow transparent precursor solution. Spin-coating 50 μl of the precursor solution on the SnO prepared in step (1) using a pipette 2 Heating the film sample on 160 deg.C heating table for 20min to obtain cesium lead bromine iodine (CsPbI) 2 Br) film, the film produced is defined as CsPbI 2 Br-5。
(3) 5mg of PDP 3T was dissolved in 1mL of chlorobenzene and stirred at 70℃for 4 hours to give a homogeneous solution, which was then applied to a 50. Mu.l-shaped syringe using a pipetteSpin-coating the L PDPP3T solution on the CsPbI prepared in the step (2) 2 On the Br-5 film, spin coating speed is 2000 rpm, acceleration is 1000 rpm, and finally silver is evaporated to serve as a top electrode.
The perovskite thin film prepared is shown in fig. 2. From fig. 2, it can be seen that a dense perovskite thin film was successfully produced. The device is used as a photoelectric detection element, and the response and detection rate results under different light wavelengths are shown in fig. 3. As can be seen from the graph, the responsivity is still as high as 0.3AW under self-powered condition under the light with the wavelength of 300-950nm -1 The specific detection rate reaches 10 13 Jones. In addition, the transparency of the film samples can reach 60% (FIG. 4). For practical applications, perovskite film stability is also important, and it can be seen from FIGS. 5 and 6 that CsPbI is subjected to high humidity 2 The Br-5 sample remained unchanged, indicating that the perovskite thin film prepared in example 1 had good stability. Furthermore, combining the SEM images of perovskite without thiamine hydrochloride added in fig. 1 with the XRD of fig. 6, it can be demonstrated that the addition and amount of thiamine hydrochloride can control the growth of perovskite and the exposure of crystal planes.
Example two
Transparent stable perovskite photodetector elements were produced according to the methods of example 1, steps (1) - (3), except that the thiamine hydrochloride amount in step (2) was changed to 10mg, and the perovskite thin film produced was defined as CsPbI 2 Br-10。
Example III
Transparent stable perovskite photodetector elements were prepared according to the methods of example 1, steps (1) - (3), except that the thiamine hydrochloride amount in step (2) was changed to 1mg, and the prepared perovskite thin film was defined as CsPbI 2 Br-1。
Example IV
Transparent stable perovskite photodetector elements were prepared according to the method of example 1, steps (1) - (3), except that the solvent volume ratio in step (2) was changed to 1:1 DMSO and DMF.
Example five
Transparent stable perovskite photodetector elements were prepared according to the method of example 1, steps (1) - (3), except that the conductive glass in step (1) was replaced with FTO conductive glass.
Example six
Transparent stable perovskite photodetector elements were prepared according to the method of example one of steps (1) - (3), except that "cesium bromide", "lead iodide" in step (2) was replaced with "cesium bromide", "lead bromide", respectively, to give cesium lead bromide (CsPbBr) 3 )。
Example seven
Transparent stable perovskite photodetector elements were prepared according to the method of example one of steps (1) - (3), except that "cesium bromide", "lead iodide" in step (2) was replaced with "cesium iodide", "lead iodide", respectively, to give cesium lead iodide (CsPbI) 3 )。
Comparative example one
Perovskite solar cells were prepared according to the procedure of example one, except that no thiamine hydrochloride was added to the perovskite precursor solution, and the perovskite thin film prepared was defined as CsPbI 2 Br. Finally, in the case of self-powered, the responsivity and specific detection rate are only 70% of those of the first embodiment. CsPbI in high humidity environment 2 The Br samples had been damaged once a day, indicating that the films prepared in embodiment one had good stability.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (7)
1. A method for preparing a transparent stable high-performance all-inorganic metal halide perovskite photoelectric detector element, which is characterized by comprising the following steps:
(1) Forming an electron transport layer on the surface of the conductive substrate;
(2) Adding lead halide, cesium halide and additives into organic solventIn the preparation, csPbI is obtained x Br y A precursor solution, wherein x+y=3;
(3) CsPbI obtained in the step (2) is processed x Br y Spin-coating the precursor solution on the surface of the electron transport layer prepared in the step (1), and heating to obtain CsPbI x Br y A thin film layer;
(4) Dissolving polythiophene-pyrrolopyrrole diketone in a benzene solvent to obtain a polythiophene-pyrrolopyrrole diketone precursor solution, and spin-coating the solution on CsPbI obtained in the step (3) x Br y The surface of the film layer;
(5) CsPbI obtained in step (4) x Br y Evaporating a metal electrode on the surface of the film layer to obtain the all-inorganic metal halogen perovskite photoelectric detector element;
the additive is selected from the group consisting of a bis-NH containing 3 + Or NH + Organic compounds of cationic groups.
2. The method of claim 1, wherein in step (1), the conductive substrate is selected from indium tin oxide or fluorine doped tin oxide conductive glass.
3. The method of claim 1, wherein in step (1), the electron transport layer material is selected from one or more of tin oxide, titanium oxide, and zinc oxide.
4. The method according to claim 1, wherein in step (2), the halogen in the lead halide or cesium halide is selected from chlorine, bromine or iodine.
5. The method according to claim 1, wherein in the step (2), the lead halide is selected from lead iodide or/and lead bromide; the cesium halide is selected from cesium iodide or/and cesium bromide.
6. The method according to claim 1, wherein in the step (4), the concentration of the polythiophene-pyrrolopyrrole dione in the benzene-based solvent is 0.1 to 7mg/mL.
7. The method of claim 1, wherein in step (5), the metal in the metal electrode is selected from gold, silver, or copper.
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