CN112490308A - Perovskite for surface passivation of photoelectric detector and preparation method thereof - Google Patents
Perovskite for surface passivation of photoelectric detector and preparation method thereof Download PDFInfo
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- CN112490308A CN112490308A CN202011312586.7A CN202011312586A CN112490308A CN 112490308 A CN112490308 A CN 112490308A CN 202011312586 A CN202011312586 A CN 202011312586A CN 112490308 A CN112490308 A CN 112490308A
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- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000002161 passivation Methods 0.000 title description 22
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims abstract description 147
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 92
- 239000000243 solution Substances 0.000 claims description 72
- 238000004140 cleaning Methods 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000012459 cleaning agent Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- -1 methylamine cation Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229940006165 cesium cation Drugs 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 76
- 230000007547 defect Effects 0.000 abstract description 12
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 238000013508 migration Methods 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- NCFBWCVNPJEZMG-UHFFFAOYSA-N [Br].[Pb].[Cs] Chemical compound [Br].[Pb].[Cs] NCFBWCVNPJEZMG-UHFFFAOYSA-N 0.000 description 9
- 230000002411 adverse Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PEKFRNRSUCMVPD-UHFFFAOYSA-L [Pb](Cl)Cl.CN Chemical compound [Pb](Cl)Cl.CN PEKFRNRSUCMVPD-UHFFFAOYSA-L 0.000 description 2
- FZHSXDYFFIMBIB-UHFFFAOYSA-L diiodolead;methanamine Chemical compound NC.I[Pb]I FZHSXDYFFIMBIB-UHFFFAOYSA-L 0.000 description 2
- MJFXORGVTOGORM-UHFFFAOYSA-L lead(2+) methanamine dibromide Chemical compound [Pb+2].[Br-].CN.[Br-] MJFXORGVTOGORM-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention especially relates to a surface-passivated perovskite for a photoelectric detector and a preparation method thereof, belonging to the technical field of crystal material processing, wherein the perovskite comprises a perovskite body, at least one surface of the perovskite body is bonded with a passivating agent, and the passivating agent is triphenylphosphine oxide; the defects caused by halogen vacancies of Cl, Br and I on the surface are passivated by forming Pb-O bonds by TPPO (triphenylphosphine oxide) and Pb in the surface of the perovskite crystal, and the surface dangling bonds of the perovskite material are reduced, so that the ion migration is reduced, and the problems of overlarge dark current and dark current drift during the operation of the perovskite photoelectric detector are effectively inhibited.
Description
Technical Field
The invention belongs to the technical field of crystal material processing, and particularly relates to a surface-passivated perovskite for a photoelectric detector and a preparation method thereof.
Background
A photodetector is a device that converts an optical signal into an electrical signal, absorbing spectral wavelengths ranging from infrared to high-energy rays. The photoelectric detector has wide application in the fields of optical imaging, optical communication, automatic control, biochemical sensing and the like. Therefore, it is of great significance to develop a photodetector with superior performance. Photodetectors mainly use semiconductor materials, and currently commercially available detector materials include silicon, germanium, indium, gallium arsenide, gallium nitride, and the like, which cover different spectral ranges due to different band gaps. Compared with the materials, the halogen perovskite has the advantages of high carrier mobility, long carrier life, high light absorption coefficient, high resistivity, adjustable forbidden band width, low raw material cost and low process cost, and is rapidly developed and applied in the photoelectric field.
The applicant finds in the course of the invention that: when the perovskite is applied to a perovskite photoelectric detector, when the perovskite photoelectric detector is in a working state, halogen ions in the perovskite can realize large-range migration through the defects and react with a metal electrode at the surface to cause the drift of the detector dark current; in addition, many leakage points are formed on the surface defect state of the perovskite material, so that the dark current of the device is increased, and the performance of the device is seriously influenced.
Disclosure of Invention
In view of the above problems, the present invention has been made to provide a perovskite for surface passivation of a photodetector and a method for preparing the same, which overcome the above problems or at least partially solve the above problems.
An embodiment of the present invention provides a surface-passivated perovskite for a photodetector, the perovskite comprising a perovskite body, at least one surface of the perovskite body being bonded with a passivating agent triphenylphosphine oxide.
Optionally, the perovskite material of the perovskite body has the chemical formula ABX3Wherein, in the step (A),
a comprises at least one of a methylamine cation, a formamidine cation, and a cesium cation;
b comprises a lead cation;
x comprises at least one of a chloride anion, a bromide anion, and an iodide anion.
Based on the same inventive concept, embodiments of the present invention also provide a method for preparing a surface-passivated perovskite for a photodetector, so as to prepare the surface-passivated perovskite for a photodetector, as described above, the method including:
obtaining the triphenylphosphine oxide;
dissolving the triphenylphosphine oxide in a solvent to obtain a triphenylphosphine oxide solution;
soaking the perovskite body in the triphenylphosphine oxide solution to obtain a primary product;
and cleaning the primary product by using a cleaning agent and airing to obtain the perovskite with the passivated surface.
Optionally, the solvent comprises toluene.
Optionally, the concentration of the triphenylphosphine oxide solution is 1mg/mL-20 mg/mL.
Optionally, the concentration of the triphenylphosphine oxide solution is 10 mg/mL.
Optionally, the perovskite body is soaked in the triphenylphosphine oxide solution for 1min to 10 min.
Optionally, the soaking time is 5 min.
Optionally, the cleaning agent comprises at least one of a toluene solution, chloroform and dichloromethane.
Optionally, during the cleaning and drying of the primary product with a cleaning agent, the cleaning time is controlled to be 1 min.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the perovskite used for surface passivation of the photoelectric detector comprises a perovskite body, wherein at least one surface of the perovskite body is bonded with a passivating agent, and the passivating agent is triphenylphosphine oxide; the defects caused by halogen vacancies of Cl, Br and I on the surface are passivated by forming Pb-O bonds by TPPO (triphenylphosphine oxide) and Pb in the surface of the perovskite crystal, and the surface dangling bonds of the perovskite material are reduced, so that the ion migration is reduced, and the problems of overlarge dark current and dark current drift during the operation of the perovskite photoelectric detector are effectively inhibited.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows cesium lead bromide (CsPbBr) provided by an embodiment of the present invention3) Optical photographs under a microscope before the perovskite single crystal is passivated;
FIG. 2 shows cesium lead bromide (CsPbBr) provided by an embodiment of the present invention3) Optical photographs under a microscope after perovskite single crystal passivation;
FIG. 3 shows cesium lead bromide (CsPbBr) provided by an embodiment of the present invention3) Fluorescence photograph under microscope under 365nm light excitation before perovskite single crystal passivation;
FIG. 4 shows cesium lead bromide (CsPbBr) provided by an embodiment of the present invention3) A fluorescence photograph under a microscope under 365nm light excitation after the perovskite single crystal is passivated;
FIG. 5 shows cesium lead bromide (CsPbBr) provided by an embodiment of the present invention3) And the perovskite single crystal is applied to an I-t curve chart of device testing after being passivated.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The applicant finds in the course of the invention that: when the perovskite is applied to a perovskite photoelectric detector, when the perovskite photoelectric detector is in a working state, halogen ions in the perovskite can realize large-range migration through the defects and react with a metal electrode at the surface to cause the drift of the detector dark current; in addition, many leakage points are formed on the surface defect state of the perovskite material, so that the dark current of the device is increased, and the performance of the device is seriously influenced. For this reason, the applicant has creatively found that: the triphenylphosphine oxide is adopted to react with the surface of the perovskite crystal, so that the dark current of the device can be reduced, and the performance of the device can be improved.
According to an exemplary embodiment of the present invention, a surface-passivated perovskite for a photodetector is provided, the perovskite comprising a perovskite body having a passivating agent bonded to at least one surface of the perovskite body, the passivating agent being triphenylphosphine oxide. In this example, the perovskite material of the perovskite body has the chemical formula ABX3Wherein A comprises a methylamine cation MA+Formamidinium FA+And cesium cation Cs+At least one of; b comprises a lead cation Pb2+(ii) a X comprises chloride anion Cl-Bromine anion Br-And iodide anion I-For example, perovskite materials of the perovskite body include, but are not limited to: cs0.87MA0.13PbBr3、MAPbBr3、CsPbBr3、MAPbBr3、FAPbBr3、CsPbBr3、MAPbCl3、CsPbI3、MAPbI3、MAPbI2Br、MAPbI2Cl and … … are not listed herein, and it should be noted that the above list is only for describing some embodiments of the present invention, and is not meant to limit the present invention.
The perovskite with the passivated surface utilizes TPPO (triphenylphosphine oxide) and Pb in the surface of the perovskite crystal to form Pb-O bonds, passivates defects caused by Cl, Br and I halogen vacancies on the surface, reduces surface dangling bonds of the perovskite material, and accordingly reduces ion migration, and effectively solves the problems of overlarge dark current and dark current drift when the perovskite photoelectric detector works.
According to another exemplary embodiment of the present invention, there is provided a method of preparing a surface-passivated perovskite for a photodetector as described above, the method comprising:
obtaining triphenylphosphine oxide;
adding triphenylphosphine oxide into a solvent to obtain a triphenylphosphine oxide solution; in the embodiment, the solvent is toluene, and the concentration of the prepared triphenylphosphine oxide solution is 1mg/mL-20 mg/mL;
soaking the perovskite body in triphenylphosphine oxide solution to obtain a primary product; in the embodiment, the perovskite body is soaked in the triphenylphosphine oxide solution for 1-10 min;
obtaining a cleaning agent; in this embodiment, the cleaning agent includes at least one of a toluene solution, chloroform, and methylene chloride
And (4) putting the primary product into a cleaning agent, cleaning and airing to obtain the perovskite with the passivated surface. In this embodiment, the cleaning time for cleaning and drying is controlled to be 1 min.
The reason why toluene is used as the solvent is: toluene is effective in dissolving TPPO (triphenylphosphine oxide) and has no dissolution damaging effect on the passivated perovskite material.
The reason for controlling the concentration of the triphenylphosphine oxide solution to be 1mg/mL-20mg/mL is that the surface passivation effect of the perovskite in the concentration range is good, the passivation efficiency is high, the adverse effect of overlarge concentration value is that a large amount of triphenylphosphine oxide (TPPO) is remained on the surface of the perovskite, and the adverse effect of undersize is that the defect passivation of the surface of the perovskite is insufficient;
the reason for controlling the time for soaking the perovskite body in the triphenylphosphine oxide solution to be 1min-10min is that the time can ensure that the surface of the perovskite completes good passivation, the adverse effect of overlarge soaking time value is that new dangling bonds and defects are easily formed on the surface, and the adverse effect of undersize is that the surface of the perovskite is insufficiently passivated;
the reason why the cleaning agent adopts the toluene solution, chloroform and dichloromethane is that the cleaning agent can dissolve and clean TPPO but not dissolve perovskite crystals, the reason why the cleaning time for cleaning and drying is controlled to be 1min is that the time is enough to clean residual TPPO solution on the surface of the perovskite, the adverse effect that the cleaning time is too large is time efficiency waste, and the adverse effect that the TPPO solution is not completely washed off is too small, so that partial TPPO remains on the surface of the crystals.
The perovskite for surface passivation of a photodetector and the method for preparing the same according to the present application will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 1 mg/mL: 3mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 1 minute, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Example 2
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 20 mg/mL: 60mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) Soaking perovskite single crystal into prepared TPPO (triphenylphosphine oxide) solutionFor 10 minutes, the surface to be treated is placed upward to allow sufficient contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Example 3
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 5 minutes, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Example 4
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, methylamine lead bromide (MAPbBr)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 5 minutes, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking methylamine lead bromide (MAPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Example 5
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, methylamine lead iodide (MAPbI)3) Soaking perovskite monocrystal into prepared TPPO (triphenyl phosphate)Phosphine oxide) for 5 minutes, the surface to be treated was placed up to make full contact with the solution.
S3, soaking methylamine lead iodide (MAPbI)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Example 6
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, methylamine lead chloride (MAPbCl)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 5 minutes, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking methylamine lead chloride (MAPbCl)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Example 7
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 5 minutes, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) The perovskite single crystal is taken out, placed in chloroform without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, and then taken out, stood and dried in the air.
Example 8
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) Soaking perovskite single crystal into prepared perovskite single crystalTPPO (triphenylphosphine oxide) solution for 5 minutes, the surface to be treated was placed up to allow sufficient contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into dichloromethane without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Comparative example 1
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 0.5 mg/mL. 1.5mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 5 minutes, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Comparative example 2
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 30 mg/mL. 90mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 5 minutes, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Comparative example 3
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) Perovskite single crystal immersionThe prepared TPPO (triphenylphosphine oxide) solution was allowed to stand for 30 seconds with the surface to be treated facing upward to allow sufficient contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Comparative example 4
S1, preparing a TPPO (triphenylphosphine oxide) solution with the solubility of 10 mg/mL. 30mg of TPPO (triphenylphosphine oxide) was weighed using a balance and added to 3mL of toluene, and left to stand for 30 minutes until it was completely dissolved.
S2, adding cesium lead bromide (CsPbBr)3) The perovskite single crystal is soaked in a prepared TPPO (triphenylphosphine oxide) solution for 15 minutes, and the surface needing to be treated is placed upwards to be in full contact with the solution.
S3, soaking cesium-lead-bromine (CsPbBr)3) Taking out the perovskite single crystal, placing the perovskite single crystal into a toluene solution without TPPO (triphenylphosphine oxide) for cleaning for 1 minute, taking out the perovskite single crystal, standing and airing.
Comparative example 5
Obtaining cesium lead bromide (CsPbBr) without passivation treatment3) A perovskite single crystal.
Related experiments:
the perovskites of examples 1-8 and comparative examples 1-5 were applied to photodetectors and tested, the results of which are shown in the following table.
In the table, the test method for the surface leakage condition is as follows: and observing the surface morphology and the light excitation condition by using an optical microscope and a fluorescence microscope.
The dark current magnitude testing method comprises the following steps: a metal electrode is deposited on the surface of a perovskite single crystal, a voltage is applied to both sides by using an electrometer, and the curve (It curve) of the crystal current with time is tested, and the magnitude of the current at 10 seconds of the applied voltage is selected as the magnitude of the dark current.
The dark current drift condition testing method comprises the following steps: a metal electrode is deposited on the surface of a perovskite single crystal, a voltage is applied to both sides using an electrometer and a curve of the crystal current with time (It curve) is tested.
The data in the analysis table can be obtained: by comparing the embodiment with the comparative example, the dark current and the drift condition of the detection device prepared by the perovskite crystal after TPPO passivation are obviously reduced and inhibited. Comparing comparative example 1 and comparative example 3 with example 3, it can be seen that the surface defects of the crystal cannot be completely passivated by soaking in a lower TPPO solution concentration for a shorter time, resulting in a device having a leakage condition, and compared with a condition without passivation treatment, the dark current is not significantly reduced, and the dark current migration is significant. Comparing comparative example 2 and comparative example 4 with example 3, it can be seen that too high TPPO solution concentration and too long soaking time can result in passivation residue on the crystal surface, which has a certain adverse effect on the performance, a certain increase in dark current, and a certain shift in dark current.
Detailed description of the drawings:
since the perovskite crystals have similarity in the change before and after TPPO (triphenylphosphine oxide) treatment, only cesium lead bromide (CsPbBr) is mentioned here3) The case of perovskite crystals is explained.
FIGS. 1 and 2 are respectively cesium lead bromide (CsPbBr) before and after passivation with TPPO (triphenylphosphine oxide)3) Photograph of perovskite crystal under optical microscope. The following pictures show that: and a plurality of scratches are distributed on the surface of the crystal before passivation, the scratches are obviously reduced after passivation, and the surface flatness is increased.
FIGS. 3 and 4 are respectively cesium lead bromide (CsPbBr) before and after passivation with TPPO (triphenylphosphine oxide)3) And (3) performing surface micro-fluorescence photo of the perovskite crystal under 365nm excitation. The following pictures show that: the surface of the crystal before passivation hardly emits light, and the surface of the crystal after passivation obviously emits light more brightly, which shows that the surface defects are reduced by passivation, the non-radiative recombination on the surface of the crystal is reduced, and the luminous efficiency is improved.
FIG. 5 is an I-t plot at-10V bias for a photodetector made from a passivated cesium lead bromide (CsPbBr3) crystal. The pictures show that: the dark current of the photoelectric detector is very small and is only in a nanoampere level; meanwhile, the dark current is stable within a certain time, and no obvious drift exists.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
compared with the conventional photoelectric detector directly prepared by using the perovskite material, the invention passivates the halogen vacancy defect on the surface of the lead-based metal halide perovskite crystal material by TPPO (triphenylphosphine oxide), effectively reduces the surface leakage and dark current of the detector, inhibits the dark current drift caused by ion migration, and obviously improves the performance of the perovskite photoelectric detector.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A surface-passivated perovskite for use in a photodetector, the perovskite comprising a perovskite body having a passivating agent triphenylphosphine oxide bonded to at least one surface of the perovskite body.
2. The surface-passivated perovskite for photodetectors according to claim 1, wherein the perovskite material of the perovskite body has the chemical formula ABX3Wherein, in the step (A),
a comprises at least one of a methylamine cation, a formamidine cation, and a cesium cation;
b comprises a lead cation;
x comprises at least one of a chloride anion, a bromide anion, and an iodide anion.
3. A method of preparing a surface-passivated perovskite for photodetectors according to claim 1 or 2, comprising:
obtaining triphenylphosphine oxide;
dissolving the triphenylphosphine oxide in a solvent to obtain a triphenylphosphine oxide solution;
soaking the perovskite body in the triphenylphosphine oxide solution to obtain a primary product;
and cleaning the primary product by using a cleaning agent and airing to obtain the perovskite with the passivated surface.
4. The method of preparing a surface-passivated perovskite for photodetectors according to claim 3, wherein the solvent comprises toluene.
5. The method of claim 3, wherein the concentration of the triphenylphosphine oxide solution is 1mg/mL-20 mg/mL.
6. The method of claim 5, wherein the concentration of the triphenylphosphine oxide solution is 10 mg/mL.
7. The method according to claim 3, wherein the perovskite body is soaked in the triphenylphosphine oxide solution for 1-10 min.
8. The method according to claim 7, wherein the soaking time is 5 min.
9. The method of claim 3, wherein the cleaning agent comprises at least one of toluene solution, chloroform and dichloromethane.
10. The method for preparing surface-passivated perovskite for photodetectors according to claim 3, wherein the cleaning time is controlled to be 1min during cleaning and drying of the primary product with a cleaning agent.
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