CN114180543B - Passivation method of black phosphorus nano-sheet, passivated black phosphorus nano-sheet and application thereof - Google Patents
Passivation method of black phosphorus nano-sheet, passivated black phosphorus nano-sheet and application thereof Download PDFInfo
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- CN114180543B CN114180543B CN202111642821.1A CN202111642821A CN114180543B CN 114180543 B CN114180543 B CN 114180543B CN 202111642821 A CN202111642821 A CN 202111642821A CN 114180543 B CN114180543 B CN 114180543B
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- tetrabutylammonium
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000002135 nanosheet Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000002161 passivation Methods 0.000 title claims abstract description 47
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 239000002064 nanoplatelet Substances 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000010931 gold Substances 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 16
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 15
- -1 gold ions Chemical class 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 8
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000002082 metal nanoparticle Substances 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000012080 ambient air Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000003570 air Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VFKKSKGQZDULMV-UHFFFAOYSA-J tetrafluoroplatinum Chemical compound F[Pt](F)(F)F VFKKSKGQZDULMV-UHFFFAOYSA-J 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PQVHMOLNSYFXIJ-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazole-3-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)C(=O)O PQVHMOLNSYFXIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/003—Phosphorus
- C01B25/006—Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electrolytic Production Of Metals (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a passivation method of a black phosphorus nano sheet, the passivated black phosphorus nano sheet and application thereof, wherein the passivation method comprises the following steps: immersing an anode and a cathode into electrolyte containing tetrabutyl cations and metal ions, and applying direct-current voltage to obtain passivated black phosphorus nano-sheet dispersion liquid; the cathode includes black phosphorus. The invention adopts a metal ion electrochemical reduction protection method, namely, black phosphorus is used as a cathode, in the stripping process, metal ions are electrochemically reduced into metal nano particles which are attached to the surface of the black phosphorus nano sheet, so that the lone pair electrons of the surface phosphorus are prevented from contacting with oxygen, the obtained black phosphorus nano sheet can stably exist in the ambient air for 15 days, even for 45 days, and the operation is simple. In addition, the black phosphorus nano-sheet device obtained by passivation can obtain stable photoelectric performance existing in the environment.
Description
Technical Field
The invention relates to the technical field of two-dimensional materials, in particular to a passivation method of a black phosphorus nano sheet, the passivated black phosphorus nano sheet and application thereof.
Background
The few-layer black phosphorus (FL-BP) has a plurality of unique properties, such as direct band gap and spectrum absorption with adjustable thickness from visible light to middle infrared band, strong exciton effect, bipolar transport property, bipolar pseudo spin semiconductor, high carrier mobility and the like, so that the BP has potential application in high-performance electronic devices, and the spectrum photoelectric detector and large-area flexible electronic devices are widened. However, one fundamental impediment to the widespread use of BP is its lack of stability under ambient conditions, as BP is very reactive towards oxygen and water, leading to rapid degradation of its electronic and optical properties.
Degradation process of the few-layer black phosphorus: 1. o generation by charge transfer reactions under ambient light 2- ；2、O 2- Dissociating at the surface and forming two P-O bonds with the black phosphazene; 3. through hydrogen bonding interactions, water molecules pull the bound oxygen out and remove P from the surface and destroy the top layer of phosphorus. The currently reported treatments for black phosphorus stabilization include covalent functionalization of aryl diazonium salts and titanesulfonic acid ligands, non-covalent functionalization of polycyclic aromatic compounds, and AlO x Surface encapsulation of inorganic materials such as graphene and boron nitride. While these methods effectively prevent oxidation of black phosphorus, their complex operational procedures limit the applicability of these methods.
CN112279228A discloses a black phosphorus nano-sheet and application of a preparation method thereof, the preparation method comprises the following steps: immersing an anode and a cathode into electrolyte containing tetrabutyl cations, and applying direct-current voltage to obtain black phosphorus nano-sheet dispersion liquid; the cathode includes black phosphorus. The electrochemical cathode stripping method is adopted, and the method can obtain the few-layer black phosphorus nano-sheets with the transverse dimensions of 10 mu m and above. However, the black phosphorus nanoplatelets obtained by stripping are extremely easy to oxidize when being kept in the air, and are difficult to store for a long time.
CN111483988A discloses a preparation method of antioxidant black phosphorus nano-sheet, comprising the following steps: adding black phosphorus nano-sheets into an organic solvent to prepare an organic solvent dispersion liquid of the black phosphorus nano-sheets, and simultaneously preparing a halogenated alkane modifying solution of alkylamine as a surface modifier; mixing the black phosphorus nano-sheet dispersion liquid and a surface modifier to obtain a mixture; placing the mixture into a sealed system heated in inert atmosphere for reflux reaction; and cooling the mixed solution, performing liquid-solid separation, washing and drying to obtain the antioxidant black phosphorus nano-sheet. The dialkyl methylamine is grafted on the surface of the black phosphorus nanosheet through a P-C-N bond, wherein P is directly connected with methylene, dialkyl amine is exposed to the outer side, and the oxidation kinetics of alkyl amine is slow, so that the oxidation of the black phosphorus nanosheet can be effectively prevented. However, the method has complicated operation steps, needs more organic reagents and has high risk.
Therefore, there is a need in the art to develop a method that is simple to operate and that can effectively prevent black phosphorus from being oxidized.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a passivation method of black phosphorus nano-sheets, which can obtain large-size and small-layer black phosphorus nano-sheets stably existing in the environment and is simple to operate.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a passivation method of a black phosphorus nano sheet, which comprises the following steps:
immersing an anode and a cathode into electrolyte containing tetrabutyl cations and metal ions, and applying direct-current voltage to obtain passivated black phosphorus nano-sheet dispersion liquid;
the cathode includes black phosphorus.
The invention adopts an electrochemical cathode stripping method, namely black phosphorus is used as an electrochemical cathode. After direct-current voltage is applied, tetrabutyl cations in the electrolyte are inserted into the black phosphorus electrode under the drive of electric field force, so that the volume of the black phosphorus electrode is greatly expanded, meanwhile, metal ions are electrochemically reduced into metal nano particles at a cathode and are attached to the surface of the black phosphorus nano sheet, the lone pair electrons on the surface of the black phosphorus nano sheet are isolated from contacting with oxygen, and the large-size black phosphorus nano sheet which can exist stably in the environment is obtained, wherein the stability period is up to 45 days.
According to the invention, researchers find that the electrochemical reduction method is more beneficial to improving the oxidation resistance of the black phosphorus nano-sheet and can obtain longer stable days compared with the reduction method by a reducing agent and the hydrogen reduction method. In addition, intercalation of tetrabutyl cation and reduction of metal ion must be performed simultaneously to obtain excellent passivation effect, otherwise the passivation effect is deteriorated.
The present invention is not particularly limited to an experimental system for providing electrochemical stripping, and any electrochemical system capable of satisfying the cathode, electrolyte and direct voltage may be used in the present invention, and a dual electrode electrochemical system may be exemplarily used.
Preferably, the metal ions comprise any one or a combination of at least two of copper ions, silver ions, platinum ions or gold ions, wherein typical but non-limiting combinations include: a combination of copper ion and silver ion, a combination of silver ion, platinum ion and gold ion, a combination of copper ion, silver ion, platinum ion and gold ion, and the like, gold ion being preferred.
Preferably, the tetrabutylammonium cation comprises tetrabutylammonium ion.
Preferably, the tetrabutyl cation is derived from a tetrabutyl quaternary ammonium salt.
Preferably, the tetrabutylammonium salt comprises any one or a combination of at least two of tetrabutylammonium acetate, tetrabutylammonium chloride, and tetrabutylammonium phosphate, wherein typical but non-limiting combinations comprise: tetrabutylammonium acetate and tetrabutylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium phosphate, tetrabutylammonium acetate, tetrabutylammonium chloride and tetrabutylammonium phosphate, etc., preferably tetrabutylammonium acetate and/or tetrabutylammonium phosphate, preferably tetrabutylammonium acetate.
Preferably, in the electrolyte, the molar concentration of the metal ion is 0.0005 to 0.01mol/L, for example, 0.0008mol/L, 0.001mol/L, 0.002mol/L, 0.003mol/L, 0.004mol/L, 0.005mol/L, 0.006mol/L, 0.007mol/L, 0.008mol/L, 0.009mol/L, etc., preferably 0.001 to 0.006mol/L, more preferably 0.002mol/L.
The concentration of the metal ions is preferably 0.001-0.006mol/L, and in the range, the passivation effect can be further improved, and the oxidation resistance of the obtained donor nano-sheet is better. The concentration of metal ions is too low, so that only a part of black phosphorus can be protected from oxidation; and too high a concentration can affect the exfoliation size, thickness, and yield of the black phosphorus nanoplatelets.
Preferably, the black phosphorus is bulk black phosphorus.
Preferably, the amount of black phosphorus in the cathode is 5-10mg, e.g., 5.5mg, 5.6mg, 5.8mg, 6.0mg, 6.2mg, 6.4mg, 6.6mg, 6.8mg, 7mg, 7.5mg, 7.8mg, 8mg, 8.3mg, 8.5mg, 8.8mg, 9mg, 9.3mg, 9.5mg, 9.7mg, etc.
Preferably, the anode comprises Pt foil.
Preferably, the solvent of the electrolyte comprises any one or a combination of at least two of N, N-Dimethylformamide (DMF), N-methyl-2-pyrrolidone, deionized water, or propylene carbonate, wherein typical but non-limiting combinations include: a combination of N, N-dimethylformamide and N-methyl-2-pyrrolidone, a combination of N-methyl-2-pyrrolidone, deionized water and propylene carbonate, a combination of N, N-dimethylformamide, N-methyl-2-pyrrolidone, deionized water or propylene carbonate, or the like, preferably N, N-dimethylformamide.
DMF is preferred as a solvent in the present invention to act as an ion diffusion medium. At the same time, DMF has a surface tension close to that of black phosphorus (about 40dyne cm -1 ) The surface binding energy can avoid the re-stacking of few layers of black phosphorus nano-sheets. In addition, DMF is an organic solvent, and a shell layer can be formed on the surface of the few-layer black phosphorus nano-sheet to prevent the DMF from contacting with oxygen molecules and water molecules in the air, so that the DMF plays a role in passivating the few-layer black phosphorus nano-sheet, and the antioxidation effect of the black phosphorus nano-sheet is further improved.
Preferably, the dc voltage is 7 to 25V, for example 7V, 8V, 10V, 12V, 14V, 15V, 16V, 18V, 20V, 22V, 24V, etc., preferably 10 to 25V, further preferably 15V.
The invention preferably has the direct-current voltage of 10-25V, and can further improve the passivation effect and the oxidation resistance of the black phosphorus nano-sheet in the voltage range. If the voltage is too low, the antioxidation effect is not obviously improved, and if the voltage is too high, the antioxidation effect is not obviously improved any more, and the resource waste is generated.
Preferably, the time for applying the direct voltage is 10-40min, for example 11min, 12min, 15min, 20min, 22min, 25min, 28min, 30min, 35min, 38min, etc., preferably 30min.
Preferably, the passivation method further comprises: after the application of the direct voltage, standing is performed.
Preferably, the time of the standing is 0.1-1h, for example 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, etc., preferably 15min.
Preferably, the passivation method further comprises: and dropwise adding the passivated black phosphorus nano sheet dispersion liquid onto the liquid level of ultrapure water, and then using a substrate to pass through the section of the passivated black phosphorus nano sheet and water to obtain the black phosphorus nano sheet dispersed on the substrate.
Preferably, the passivated black phosphorus nanoplatelet dispersion is injected drop by drop onto the surface of ultrapure water by a pipette.
Preferably, the pipette has a volume of 10 μl.
Preferably, the total amount of injection is 50 μl.
Preferably, the substrate is SiO 2 A Si substrate. SiO & lt- & gt 2 By Si substrate is meant a substrate having a surface comprising a layer of amorphous SiO 2 Is a silicon wafer.
Preferably, the SiO 2 Oxide layer SiO on surface of Si substrate 2 Is 300nm thick.
The second object of the present invention is to provide a passivated black phosphorus nanoplatelet obtained by the passivation method according to one of the objects.
Preferably, the number of layers of the passivated black phosphorus nano-sheet is less than or equal to 10, such as 1 layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers or 9 layers, and the like, preferably less than or equal to 8.
Preferably, the thickness of the passivated black phosphorus nanoplatelets is 2-7nm, such as 2.1nm, 2.3nm, 2.5nm, 2.7nm, 2.9nm, 3.1nm, 3.3nm, 3.5nm, 3.7nm, 3.9nm, 4.1nm, 4.3nm, 4.5nm, 4.7nm, 4.9nm, 5.1nm, 5.3nm, 5.5nm, 5.7nm, 5.9nm, 6.1nm, 6.3nm, 6.5nm, 6.7nm, 6.9nm, etc., preferably 2-4nm.
Preferably, the passivated black phosphorus nanoplatelets have a lateral dimension of ∈10 μm, e.g. 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, etc., preferably 10-100 μm. The lateral dimension refers to the maximum diameter of the nanoplatelets in two dimensions (non-thickness directions).
Preferably, the passivated black phosphorus nanoplatelets are stored in air for a period of 15 or more days, such as 15, 18, 21, 24, 27, 30, 33, 36, 39, 42, 45, etc., preferably 30 or more days, further preferably 45 or more days.
The invention further aims to provide an application of the passivated black phosphorus nano-sheet in preparing a semiconductor integrated photoelectric device, an optical film, a gas sensor, a biosensor, a solar cell or electronic printing.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a metal ion electrochemical reduction protection method, namely, black phosphorus is used as a cathode, in the stripping process, metal ions are electrochemically reduced into metal nano particles which are attached to the surface of the black phosphorus nano sheet, so that the lone pair electrons of the surface phosphorus are prevented from contacting with oxygen, the obtained black phosphorus nano sheet can stably exist in the ambient air for more than 5 days, basically up to 15 days, even up to 45 days, and the operation is simple.
(2) The black phosphorus nano-sheet device obtained by passivation can obtain stable photoelectric performance in the environment.
Drawings
Fig. 1 is a schematic diagram of experimental preparation of passivation of black phosphorus nanoplatelets in an embodiment of the present invention.
Fig. 2a is a raman spectrum comparison graph of the gold nanoparticle-protected black phosphorus nanoplatelets and unpassivated black phosphorus nanoplatelets obtained in example 1 of the present invention.
FIG. 2b shows the Raman characteristic peaks of the black phosphorus nanoplatelets obtained in example 1 of the present invention, which are protected for 45 days by gold nanoparticles.
FIG. 3a is an AFM atomic force microscope characterization of the black phosphorus nanoplatelets obtained in example 1 in air for 1 day.
Fig. 3b is an AFM atomic force microscope characterization of the black phosphorus nanoplatelets obtained in example 1 after 10 days of air.
Fig. 3c is an AFM atomic force microscope characterization of the black phosphorus nanoplatelets obtained in example 1 in air for 25 days.
Fig. 3d is an AFM atomic force microscope characterization of the black phosphorus nanoplatelets obtained in example 1 when left in air for 45 days.
Fig. 4a is an optical photograph of the black phosphorus nanoplatelets obtained in example 1, left in air for 1 day.
Fig. 4b is an optical photograph of the black phosphorus nanoplatelets obtained in example 1, which were left in air for 10 days.
Fig. 4c is an optical photograph of the black phosphorus nanoplatelets obtained in example 1, placed in air for 25 days.
Fig. 4d is an optical photograph of the black phosphorus nanoplatelets obtained in example 1 left in air for 45 days.
FIG. 5a shows the source-drain current I of the black phosphorus nanoplatelets obtained in example 1 ds With source-drain bias voltage V ds Is a change curve of (a).
Fig. 5b is a graph of the photoelectric response of the black phosphorus nanoplatelets obtained in example 1 from visible to mid-infrared laser excitation.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the passivation method of the black phosphorus nanosheets provided in the following embodiments of the present invention, the power supply is an adjustable dc voltage-stabilizing and current-stabilizing power supply, which can provide a voltage of 0-27V, it should be clear to a person skilled in the art that the adjustable dc voltage-stabilizing and current-stabilizing power supply can be replaced by other dc power supplies, and only the same dc voltage provided by the adjustable dc voltage-stabilizing and current-stabilizing power supply as in the embodiments needs to be ensured.
The passivation methods of the few-black phosphorus nanoplatelets provided in the following examples of the present invention were all performed in glass beakers having a volume of 50mL.
FIG. 1 shows a schematic diagram of the experimental preparation of the passivation method of the few-layer black phosphorus nanoplatelets in the following examples, in which a dual electrode system was used. After direct current voltage is applied to the electrochemical system, metal ions are electrochemically reduced into metal nano particles and attached to the surface of the black phosphorus nano sheet.
Example 1
The embodiment provides a passivation method of a black phosphorus nano-sheet, which specifically comprises the following steps:
(1) 6mg of tetrabutylammonium acetate (CH) was measured with an electronic balance 3 COO.TBA), 7.4mg of gold acetate ((CH) 3 COO) 3 Au), adding the gold particles into a glass beaker containing 10mL of an organic solvent DMF, and oscillating for 1min in an ultrasonic cleaner to obtain an electrolyte with the gold particle concentration of 0.002 mol/L;
(2) Placing 5mg of block black phosphorus (purchased from Yu Muke nanometer company, purity is more than 99.999%) on a tetrafluoroplatinum sheet electrode clamp, connecting with a direct current power supply negative electrode, taking Pt as an electrochemical cathode and an electrochemical anode, wherein the two electrodes are kept parallel, and the distance between the two electrodes is 2cm;
(3) Immersing the bulk black phosphorus and Pt in the step (2) into the electrolyte in the step (1);
(4) And (3) applying a direct-current voltage of 15V to the electrochemical system, and obtaining the black phosphorus nano-sheet dispersion liquid protected by the gold nanoclusters after 30min.
Examples 2 to 3
The difference from example 1 is that in step (1), gold acetate is replaced with copper acetate (example 2) and silver acetate (example 3) in the same amounts.
Examples 4 to 9
The difference from example 1 was that 3.7mg (example 4), 14.8mg (example 5), 1.85mg (example 6), 18.5mg (example 7), 22.2mg (example 8), 37mg (example 9) of gold acetate were weighed by an electronic balance in step (1), and electrolytes having concentrations of 0.001mol/L (example 4), 0.004mol/L (example 5), 0.0005mol/L (example 6), 0.005mol/L (example 7), 0.006mol/L (example 8), and 0.01mol/L (example 9) were obtained.
Examples 10 to 12
The difference from example 1 is that in step (4), the time for applying the 15V dc voltage is 10min (example 10), 20min (example 11), 40min (example 12).
Examples 13 to 17
The difference from example 1 is that in step (4), direct current voltages of 7V (example 13), 10V (example 14), 15V (example 15), 25V (example 16), 30V (example 17) are applied to the electrochemical system.
Comparative example 1
The comparative example provides a passivation method of black phosphorus nano-sheets, which comprises the following steps:
(1) 6mg of tetrabutylammonium acetate (CH) was measured with an electronic balance 3 COO.TBA), adding into a glass beaker containing 10mL of an organic solvent DMF, and oscillating for 1min in an ultrasonic cleaner to obtain an electrolyte with the concentration of 0.002 mol/L;
(2) Placing 5mg of block black phosphorus (purchased from Yu Muke nanometer company, purity is more than 99.999%) on a tetrafluoroplatinum sheet electrode clamp, connecting with a direct current power supply negative electrode, taking Pt as an electrochemical cathode and an electrochemical anode, wherein the two electrodes are kept parallel, and the distance between the two electrodes is 2cm;
(3) Immersing the bulk black phosphorus and Pt in the step (2) into the electrolyte in the step (1);
(4) Applying a direct current voltage of 15V to the electrochemical system for 30min to obtain black phosphorus nano-sheet dispersion liquid;
(5) Adding 0.002mol/L of gold acetate ((CH) to the dispersion obtained in the step (4) 3 COO) 3 Au) and 0.0005mol/L reducer (ethylene glycol), stirring for 1h to obtain the passivated black phosphorus nano-sheet dispersion.
Comparative example 2
The comparative example provides a passivation method of black phosphorus nano-sheets, which comprises the following steps:
(1) 6mg of tetrabutylammonium acetate (CH) was measured with an electronic balance 3 COO TBA), 10mL of an organic solvent was addedOscillating for 1min in a glass beaker of DMF in an ultrasonic cleaner to obtain electrolyte with gold particle concentration of 0.002 mol/L;
(2) Placing 5mg of block black phosphorus (purchased from Yu Muke nanometer company, purity is more than 99.999%) on a tetrafluoroplatinum sheet electrode clamp, connecting with a direct current power supply negative electrode, taking Pt as an electrochemical cathode and an electrochemical anode, wherein the two electrodes are kept parallel, and the distance between the two electrodes is 2cm;
(3) Immersing the bulk black phosphorus and Pt in the step (2) into the electrolyte in the step (1);
(4) Applying a direct current voltage of 15V to the electrochemical system, stopping applying the voltage after 30min, and adding 0.002mol/L of gold acetate to obtain black phosphorus nano-sheet dispersion liquid;
(5) Injecting the black phosphorus nano-sheet dispersion liquid obtained in the step (4) dropwise onto the liquid surface of ultrapure water through a liquid-transferring gun, and then using SiO 2 The Si substrate passes through the cross section of the black phosphorus nano sheet and water to obtain the black phosphorus nano sheet dispersed on the substrate;
(6) Placing the black phosphorus nano-sheets dispersed on the substrate into a CVD furnace, heating to 300 ℃ and introducing 100sccm H 2 And (3) carrying out hydrogen reduction to obtain the passivated black phosphorus nano-sheet.
Test example 1
The following performance tests were performed on the black phosphorus nanoplatelet dispersion obtained in example 1:
standing the black phosphorus nanoplatelet dispersion obtained in the step (4) in the example 1 for 0.5h to enable thick-layer black phosphorus nanoplatelets to be deposited, and performing sample preparation by using the upper-layer dispersion, namely transferring the black phosphorus nanoplatelets in the upper-layer dispersion to 300nm SiO 2 on/Si, the prepared samples were tested as follows:
(1) raman spectroscopy
Test instrument: microscopic confocal laser raman spectrometer of ranishao company, uk, model In via Reflex, test conditions: the excitation light wavelength was 514nm at room temperature.
FIG. 2a is a graph showing the Raman spectrum comparison of gold nanoparticle-protected black phosphorus nanoplatelets and unpassivated black phosphorus nanoplatelets obtained in example 1, the gold nanoparticle-protected black phosphorus nanoplatelets being respectivelyAt 360.8cm -1 ，438.0cm -1 And 466.8cm -1 Obvious Raman characteristic peaks are observed, which respectively correspond to A of black phosphorus crystals 1 g ，A 2g And A 2 g Vibration mode, indicating that flakes in the dispersion obtained in example 1 remain as black phosphorus crystals; the same sample was then tested for raman spectra on different days, and it can be observed from the test results of fig. 2b that after 30 days the sample still shows three characteristic peaks of black phosphorus, and a g 1 /A g 2 Greater than 0.4.
(2) AFM atomic force microscope characterization
Test instrument: atomic force microscope of bruck company, model number Dimension ICON, test conditions: room temperature, intelligent mode.
FIGS. 3a, 3b, 3c and 3d are AFM atomic force microscope characterization graphs of the black phosphorus nanoplatelets obtained in example 1 for various times in air, it can be seen that the thickness of the black phosphorus is 3.2nm, and that the black phosphorus nanoplatelets protected by the metal nanoclusters do not undergo any oxidation during shooting for up to 45 days;
(3) optical microscope characterization
Test instrument: optical microscope of Shanghai Cai Kang optical instruments Co., ltd., model 9XB-PC, test conditions: room temperature.
Fig. 4a, 4b, 4c and 4d are optical photographs of the black phosphorus nanoplatelets obtained in example 1, which were left in the air for different times, and it can be seen that the gold nanoparticle-protected black phosphorus nanoplatelets have a lateral dimension of 55 μm, and the black phosphorus nanoplatelets were not oxidized at all for 45 days of continuous photographing.
(4) Photoelectric performance test
Test instrument: test source table (KEITHLEY 2614B) and laser signal generator (RIGOL DG 1022), test conditions: room temperature.
FIGS. 5a and 5b are photoelectric data images of the black phosphorus nanoplatelets obtained in example 1, from which FIG. 5a it can be seen that the source-drain current I of the black phosphorus nanoplatelets ds With source-drain bias voltage V ds The increase in (a) is in a linear growth mode, indicating that the device operates in the linear region under this test parameter, indicating good ohmic contactThe contact characteristics do not create significant additional resistance at the interface. And the bias current measured is greatest when the gate voltage is-60V, and is smallest when the gate voltage is 60V as the gate voltage changes from-60V to 60V. The output characteristic curve relationship of the typical P-type semiconductor is met. Fig. 5b shows that the black phosphorus nanoplatelets all have a significant photoelectric response under excitation from visible light to mid-infrared laser.
Test example 2:
standing the black phosphorus nanosheet dispersion solutions obtained in examples 1-17 and comparative examples 1-2 for 0.5h, respectively, wherein after the thick-layer black phosphorus nanosheets are deposited, taking a supernatant liquid sample of the dispersion solution, and transferring the black phosphorus nanosheets in the black phosphorus dispersion solution to 300nm SiO 2 on/Si, the following performance tests were performed:
the preservation time of the black phosphorus nano-sheet is as follows: shooting the black phosphorus nano-sheets in the above embodiments respectively under an optical microscope for different days, and observing the preservation time of the few-layer black phosphorus in the different embodiments; the number of days that the black phosphorus nanoplatelets changed was recorded. (oxidation is generated when small bubbles are generated on the surface of the black phosphorus nano-sheet)
The test results are shown in table 1:
TABLE 1
| Black phosphorus nano-sheet | Days of preservation | Black phosphorus nano-sheet | Days of storage/day |
| Example 1 | 45 | Example 11 | 30 |
| Example 2 | 30 | Example 12 | 45 |
| Example 3 | 45 | Example 13 | 5 |
| Example 4 | 15 | Example 14 | 15 |
| Example 5 | 45 | Example 15 | 45 |
| Example 6 | 7 | Example 16 | 45 |
| Example 7 | 45 | Example 17 | 45 |
| Example 8 | 45 | Comparative example 1 | 10 |
| Example 9 | 45 | Comparative example 2 | 20 |
| Example 10 | 15 |
As shown in Table 1, the black phosphorus nanoplatelets obtained by the passivation method provided by the invention have excellent oxidation resistance, and can be stored for a long time in an air environment, wherein the storage time is more than 5 days, more than 15 days basically and up to 45 days.
The chemical reducing agent used in comparative example 1 can damage black phosphorus to a certain extent, so that a plurality of holes appear on the surface of the black phosphorus nano-sheet, the performance of the black phosphorus nano-sheet is affected, and the oxidation resistance is reduced. Comparative example 2 was reduced by heating at high temperature and introducing hydrogen, and the passivation effect was not as good as that of the example.
As is clear from comparative examples 1 to 3, the kinds of metal ions incorporated in the electrolyte are different, and the protection effect on the black phosphorus nanoplatelets is greatly different, and the protection effect is the best when the metal nanoclusters are gold (example 1), copper (example 2) and silver (example 3), wherein the gold nanoclusters are the best.
As is clear from comparative examples 1 and 4 to 9, the higher the concentration of metal ions, the more metal nanoclusters are obtained, and the better the protection effect on the black phosphorus nanoplatelets, but when the concentration of metal ions is too high, the peeling of the black phosphorus nanoplatelets is affected, and the obtained black phosphorus nanoplatelets have low yield, small size and thick thickness, preferably the concentration is 0.001 to 0.006mol/L, more preferably 0.002 to 0.006mol/L, and most preferably 0.002mol/L.
As is clear from comparative examples 1 and 10 to 12, the longer the peeling time, the more metal nanoclusters are obtained by electrochemical reduction, and the better the effect of protecting the black phosphorus nanoplatelets.
As is clear from comparative examples 1, 13 to 17, the higher the voltage, the faster and more metal ions are reduced, and the better the protection effect is; however, when the voltage is too large, the stripping of the black phosphorus nano-sheet is affected, the obtained black phosphorus nano-sheet has small size and thick thickness, the preservation time is not increased any more, and the energy waste is caused.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (19)
1. A passivation method of black phosphorus nanoplatelets, characterized in that the passivation method comprises the following steps:
immersing an anode and a cathode into electrolyte containing tetrabutyl cations and metal ions, and applying direct-current voltage to obtain passivated black phosphorus nano-sheet dispersion liquid;
the cathode comprises black phosphorus;
in the electrolyte, the molar concentration of metal ions is 0.002-0.006mol/L;
the metal ions are gold ions;
the direct current voltage is 15-25V;
the time for applying the direct current voltage is 20-40min.
2. The passivation method according to claim 1, characterized in that the molar concentration of metal ions in the electrolyte is 0.002mol/L.
3. The passivation method of claim 1, wherein the tetrabutylammonium cation comprises a tetrabutylammonium ion.
4. The passivation method of claim 1, wherein the tetrabutyl cation is derived from a tetrabutyl quaternary ammonium salt.
5. The passivation method according to claim 4, wherein the tetrabutylammonium salt comprises any one or a combination of at least two of tetrabutylammonium acetate, tetrabutylammonium chloride and tetrabutylammonium phosphate.
6. The passivation method according to claim 5, characterized in that the tetrabutylammonium salt is tetrabutylammonium acetate and/or tetrabutylammonium phosphate.
7. The passivation method according to claim 6, wherein the tetrabutylammonium salt is tetrabutylammonium acetate.
8. The passivation method of claim 1, wherein the black phosphorus is bulk black phosphorus.
9. A passivation method according to claim 1, characterized in that the amount of black phosphorus in the cathode is 5-10mg.
10. A passivation method according to claim 1, characterized in that the anode comprises a Pt foil.
11. The passivation method according to claim 1, wherein the solvent of the electrolyte comprises any one or a combination of at least two of N, N-dimethylformamide, N-methyl-2-pyrrolidone, deionized water, or propylene carbonate.
12. The passivation method according to claim 11, characterized in that the solvent of the electrolyte is N, N-dimethylformamide.
13. A passivation method according to claim 1, characterized in that the dc voltage is 15V.
14. A passivation method according to claim 1, characterized in that the time for applying the direct voltage is 30min.
15. The passivation method according to claim 1, characterized in that the passivation method further comprises: after the application of the direct voltage, standing is performed.
16. A passivation method according to claim 15, characterized in that the time of rest is 0.1-1h.
17. A passivation method according to claim 16, characterized in that the time of rest is 15min.
18. The passivation method according to claim 1, characterized in that the passivation method further comprises: and dropwise adding the passivated black phosphorus nanosheet dispersion liquid onto the liquid level of ultrapure water, and then using the substrate to pass through the section of the passivated black phosphorus nanosheets and water to obtain the black phosphorus nanosheets dispersed on the substrate.
19. The passivation method according to claim 18, wherein the passivated black phosphorus nanoplatelets dispersion is injected drop-wise onto the surface of the ultra pure water by a pipette.
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