CN114180543A - Passivation method of black phosphorus nanosheet, passivated black phosphorus nanosheet and application thereof - Google Patents
Passivation method of black phosphorus nanosheet, passivated black phosphorus nanosheet and application thereof Download PDFInfo
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- CN114180543A CN114180543A CN202111642821.1A CN202111642821A CN114180543A CN 114180543 A CN114180543 A CN 114180543A CN 202111642821 A CN202111642821 A CN 202111642821A CN 114180543 A CN114180543 A CN 114180543A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000002135 nanosheet Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000002161 passivation Methods 0.000 title claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 239000010931 gold Substances 0.000 claims description 20
- -1 silver ions Chemical class 0.000 claims description 20
- 229910052737 gold Inorganic materials 0.000 claims description 18
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 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
- 239000002055 nanoplate Substances 0.000 claims description 7
- 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
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
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- 239000004065 semiconductor Substances 0.000 claims description 4
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- 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
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- 238000012360 testing method Methods 0.000 description 16
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- 230000000694 effects Effects 0.000 description 13
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 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
- 239000002105 nanoparticle Substances 0.000 description 5
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- VFKKSKGQZDULMV-UHFFFAOYSA-J tetrafluoroplatinum Chemical compound F[Pt](F)(F)F VFKKSKGQZDULMV-UHFFFAOYSA-J 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
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- 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
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
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- 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect 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
- 238000004299 exfoliation Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
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- 238000006467 substitution reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Images
Classifications
-
- 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
Abstract
The invention relates to a passivation method of black phosphorus nanosheets, the passivated black phosphorus nanosheets and application thereof, wherein the passivation method comprises the following steps: immersing the anode and the cathode into electrolyte containing tetrabutyl cations and metal ions, and applying direct-current voltage to obtain passivated black phosphorus nanosheet 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 to be attached to the surfaces of black phosphorus nano sheets, the contact between lone-pair electrons of surface phosphorus and oxygen is prevented, the obtained black phosphorus nano sheets can stably exist in ambient air for 15 days, even 45 days, and the operation is simple. In addition, the black phosphorus nanosheet device obtained through 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 black phosphorus nanosheets, the passivated black phosphorus nanosheets and application thereof.
Background
The few-layer black phosphorus (FL-BP) has many unique properties such as adjustable direct band gap and spectrum absorption from visible light to middle infrared band thickness, strong exciton effect, bipolar transport characteristics, bipolar pseudo spin semiconductors, high carrier mobility and the like, so that the BP has potential application in high-performance electronic devices, and a spectrum photoelectric detector and a large-area flexible electronic device are widened. However, one fundamental impediment to the widespread use of BP is its lack of stability under ambient conditions, since BP is very reactive to oxygen and water, resulting in rapid degradation of its electronic and optical properties.
And (3) degrading the few-layer black phosphorus: 1. o generation by charge transfer reactions under ambient light2-；2、O2-Dissociating on the surface and forming two P-O bonds with the black phosphorus alkene; 3. through hydrogen bonding interactions, water molecules draw bonded oxygen out and remove P from the surface and destroy the top layer of phosphorus. The currently reported black phosphorus stabilization treatment methods include covalent functionalization of aryl diazonium salts and titanium sulfonic acid ligands, non-covalent functionalization of polycyclic aromatic compounds, and AlOxAnd surface packaging of inorganic materials such as graphene and boron nitride. Although these methods are effective in preventing the oxidation of black phosphorus, their complicated procedures limit the application of these methods.
CN112279228A discloses a black phosphorus nanosheet and application of the preparation method thereof, wherein 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 nanosheet dispersion liquid; the cathode includes black phosphorus. An electrochemical cathode stripping method is adopted, and the method can obtain few-layer black phosphorus nanosheets with the transverse dimension of 10 mu m or more. However, the black phosphorus nanosheet obtained by stripping is extremely easy to oxidize after being left in the air, and is difficult to store for a long time.
CN111483988A discloses a preparation method of an antioxidant black phosphorus nanosheet, which comprises the following steps: adding the black phosphorus nanosheet into an organic solvent to prepare an organic solvent dispersion liquid of the black phosphorus nanosheet, and simultaneously preparing a halogenated alkane modification solution of alkylamine as a surface modifier; mixing the black phosphorus nanosheet dispersion liquid with a surface modifier to obtain a mixture; placing the mixture in a sealed system heated in inert atmosphere for reflux reaction; and cooling the mixed solution, and then carrying out liquid-solid separation, washing and drying to obtain the antioxidant black phosphorus nanosheet. Dialkyl alkyl 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 outside, the oxidation kinetics of the alkyl amine is slow, and the oxidation of the black phosphorus nanosheet can be effectively prevented. However, this method is complicated in operation steps and requires a large amount of organic reagents, which is highly dangerous.
Therefore, there is a need in the art to develop a method that is simple to operate and can effectively prevent black phosphorus from being oxidized.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the present invention is to provide a black phosphorus nanosheet passivation method, which can obtain a black phosphorus nanosheet with a large size and few layers, which stably exists in the environment, and is simple to operate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a passivation method of black phosphorus nanosheets, which comprises the following steps:
immersing the anode and the cathode into electrolyte containing tetrabutyl cations and metal ions, and applying direct-current voltage to obtain passivated black phosphorus nanosheet 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 expanded violently, and meanwhile, metal ions are electrochemically reduced into metal nanoparticles at the cathode and attached to the surface of the black phosphorus nanosheet, lone pair electrons on the surface of the black phosphorus nanosheet are isolated from being contacted with oxygen, so that the large-size black phosphorus nanosheet which can stably exist in the environment is obtained, and the number of stable days is up to 45 days.
The researchers of the invention find that compared with the methods of reducing agent reduction and hydrogen reduction, the method of electrochemical reduction is more beneficial to improving the oxidation resistance of the black phosphorus nanosheet and can obtain longer stable days. In addition, the intercalation of the tetrabutyl cation and the reduction of the metal ion must be performed simultaneously to obtain an excellent passivation effect, otherwise the passivation effect is deteriorated.
The experimental system for providing electrochemical peeling is not particularly limited, and any electrochemical system satisfying the cathode, the electrolyte and the dc voltage may be used in the present invention, and a two-electrode electrochemical system may be used as an exemplary system.
Preferably, the metal ions include 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 ions and silver ions, a combination of silver ions, platinum ions and gold ions, a combination of copper ions, silver ions, platinum ions and gold ions, and the like, with gold ions being preferred.
Preferably, the tetrabutyl cation comprises a tetrabutylammonium ion.
Preferably, the tetrabutyl cation is derived from tetrabutyl quaternary ammonium salt.
Preferably, the tetrabutyl quaternary ammonium 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 include: a combination of tetrabutylammonium acetate and tetrabutylammonium chloride, a combination of tetrabutylammonium chloride and tetrabutylammonium phosphate, a combination of tetrabutylammonium acetate, tetrabutylammonium chloride and tetrabutylammonium phosphate, and the like, with tetrabutylammonium acetate and/or tetrabutylammonium phosphate being preferred, and tetrabutylammonium acetate being preferred.
Preferably, the molar concentration of the metal ions in the electrolyte is 0.0005 to 0.01mol/L, such as 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, and more preferably 0.002 mol/L.
In the invention, the concentration of the metal ions is preferably 0.001-0.006mol/L, and within the range, the passivation effect can be further improved, and the obtained forest nano-sheet has better oxidation resistance. The metal ion concentration is too low, and only part of black phosphorus can be protected from being oxidized; while too high a concentration can affect the peel size, thickness and yield of the black phosphorus nanoplate.
Preferably, the black phosphorus is bulk black phosphorus.
Preferably, the amount of black phosphorus in the cathode is 5-10mg, such as 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, and the like.
Preferably, the anode comprises a Pt foil.
Preferably, the solvent of the electrolyte comprises any one or at least two combinations 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, with N, N-dimethylformamide being preferred.
DMF is preferably used as a solvent in the invention and plays a role of an ion diffusion medium. At the same time, the surface tension of DMF is close to that of black phosphorus (about 40dyne cm)-1) The surface binding energy can avoid the restacking of few layers of black phosphorus nano sheets. In addition, DMF is an organic solvent, and can form an organic shell layer on the surface of the few-layer black phosphorus nanosheet, so that the organic shell layer is prevented from contacting with oxygen molecules and water molecules in the air, the effect of passivating the few-layer black phosphorus nanosheet is achieved, and the antioxidant effect of the black phosphorus nanosheet is further improved.
Preferably, the dc voltage is 7-25V, such as 7V, 8V, 10V, 12V, 14V, 15V, 16V, 18V, 20V, 22V, 24V, etc., preferably 10-25V, more preferably 15V.
The direct current voltage is preferably 10-25V, and the passivation effect can be further improved within the voltage range, so that the oxidation resistance effect of the black phosphorus nanosheet is improved. If the voltage is too low, the anti-oxidation effect is not obviously improved, and if the voltage is too high, the anti-oxidation effect is not obviously improved any more, so that the resource waste is generated.
Preferably, the time for applying the direct current voltage is 10-40min, such as 11min, 12min, 15min, 20min, 22min, 25min, 28min, 30min, 35min, 38min, etc., preferably 30 min.
Preferably, the passivation method further comprises: after the application of the dc voltage, a standing was performed.
Preferably, the time of standing is 0.1-1h, such as 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, etc., preferably 15 min.
Preferably, the passivation method further comprises: and dropwise adding the passivated black phosphorus nanosheet dispersion liquid onto the liquid level of ultrapure water, and then penetrating the cross section of the passivated black phosphorus nanosheet and water by using a substrate to obtain the black phosphorus nanosheet dispersed on the substrate.
Preferably, the passivated black phosphorus nanosheet dispersion is injected drop-wise onto the surface of ultrapure water by a pipette.
Preferably, the volume of the pipette is 10 μ L.
Preferably, the total amount of the injection is 50 μ L.
Preferably, the substrate is SiO2a/Si substrate. "SiO2The term "Si substrate" means a substrate having a surface comprising a layer of amorphous SiO2The silicon wafer of (1).
Preferably, the SiO2SiO (silicon oxide) layer on surface of Si substrate2Is 300 nm.
The second object of the present invention is to provide a passivated black phosphorus nanosheet obtained by the passivation method described in the first object.
Preferably, the number of the layers of the passivated black phosphorus nanosheets 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 nanoplates 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 2-4 nm.
Preferably, the transverse dimension of the passivated black phosphorus nanosheets is ≧ 10 μm, such as 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, and the like, preferably 10-100 μm. The transverse dimension refers to the maximum diameter of the nanoplatelets in two dimensions (non-thickness direction).
Preferably, the number of days of the passivated black phosphorus nanosheets stored in the air is greater than or equal to 15 days, such as 15 days, 18 days, 21 days, 24 days, 27 days, 30 days, 33 days, 36 days, 39 days, 42 days, 45 days and the like, preferably greater than or equal to 30 days, and more preferably greater than or equal to 45 days.
The third purpose of the invention is to provide the application of the passivated black phosphorus nanosheet in the second purpose in preparing semiconductor integrated photoelectric devices, optical films, gas sensors, biosensors, solar cells 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 to be attached to the surfaces of black phosphorus nano sheets, the contact between lone-pair electrons of surface phosphorus and oxygen is prevented, the obtained black phosphorus nano sheets can stably exist in ambient air for more than 5 days, basically can reach 15 days, even can reach 45 days, and the operation is simple.
(2) The black phosphorus nanosheet device obtained through passivation can obtain stable photoelectric performance existing in the environment.
Drawings
Fig. 1 is a schematic diagram of experimental preparation of black phosphorus nanosheet passivation in an embodiment of the present invention.
Fig. 2a is a comparison graph of raman spectra of black phosphorus nanosheets protected with gold nanoparticles obtained in example 1 of the present invention and black phosphorus nanosheets without passivation.
Fig. 2b is a raman characteristic peak of the black phosphorus nanosheet protected by the gold nanoparticles for 45 days obtained in example 1 of the present invention.
FIG. 3a is an AFM atomic force microscope characterization chart of the black phosphorus nanosheets obtained in example 1 after being placed in air for 1 day.
Fig. 3b is an AFM atomic force microscope characterization chart of the black phosphorus nanosheet obtained in example 1, placed in air for 10 days.
Fig. 3c is an AFM atomic force microscope characterization chart of the black phosphorus nanosheets obtained in example 1, left in air for 25 days.
Fig. 3d is an AFM atomic force microscope characterization chart of the black phosphorus nanosheets obtained in example 1 after being placed in air for 45 days.
Fig. 4a is an optical photograph of the black phosphorus nanosheet obtained in example 1, after being left in air for 1 day.
Fig. 4b is an optical photograph of the black phosphorus nanosheet obtained in example 1, after being left in air for 10 days.
Fig. 4c is an optical photograph of the black phosphorus nanosheet obtained in example 1, when left in air for 25 days.
Fig. 4d is an optical photograph of the black phosphorus nanosheet obtained in example 1, after being left in air for 45 days.
FIG. 5a shows the source-drain current I of the black phosphorus nanosheet obtained in example 1dsWith source drain bias voltage VdsThe change curve of (2).
Fig. 5b is a photoelectric response diagram of the black phosphorus nanosheet obtained in example 1 under excitation from visible light to mid-infrared laser light.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the passivation method of the black phosphorus nanosheet provided in the following embodiment 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, and it should be understood by those 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 dc voltage provided by the adjustable dc voltage-stabilizing and current-stabilizing power supply needs to be the same as that in the embodiment.
The passivation methods of the black phosphorus-less nanosheets provided by the following examples of the present invention were all performed in a glass beaker having a volume of 50 mL.
Fig. 1 shows a schematic diagram of experimental preparation of the passivation method of few-layer black phosphorus nanosheets in the following examples, and a two-electrode system is used in the preparation. After a direct current voltage is applied to the electrochemical system, metal ions are electrochemically reduced into metal nanoparticles and attached to the surfaces of the black phosphorus nanosheets.
Example 1
The embodiment provides a passivation method of a black phosphorus nanosheet, which specifically comprises the following steps:
(1) 6mg of tetrabutylammonium acetate (CH) are metered in by an electronic balance3COO TBA), 7.4mg of gold acetate ((CH)3COO)3Au), adding the gold particles into a glass beaker containing 10mL of organic solvent DMF, and oscillating the glass beaker in an ultrasonic cleaner for 1min to obtain an electrolyte with the gold particle concentration of 0.002 mol/L;
(2) 5mg of block black phosphorus (purchased from Muscow Nana, purity > 99.999%) is placed on a tetrafluoro platinum sheet electrode clamp, is connected with a negative electrode of a direct current power supply and is used as an electrochemical cathode, Pt is used as an electrochemical anode, the two electrodes are kept in parallel, and the distance between the electrodes is 2 cm;
(3) immersing the block 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 nanosheet dispersion protected by the gold nanoclusters after 30 min.
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 equal amounts.
Examples 4 to 9
The difference from example 1 is that in step (1), 3.7mg (example 4), 14.8mg (example 5), 1.85mg (example 6), 18.5mg (example 7), 22.2mg (example 8) and 37mg (example 9) of gold acetate were measured by an electronic balance to obtain 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).
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) and 40min (example 12).
Examples 13 to 17
The difference from example 1 is that, in step (4), dc voltages of 7V (example 13), 10V (example 14), 15V (example 15), 25V (example 16), and 30V (example 17) were applied to the electrochemical system.
Comparative example 1
The comparative example provides a passivation method of black phosphorus nanosheets, which specifically comprises the following steps:
(1) 6mg of tetrabutylammonium acetate (CH) are metered in by an electronic balance3COO.TBA), adding the mixture into a glass beaker containing 10mL of organic solvent DMF, and oscillating the glass beaker in an ultrasonic cleaner for 1min to obtain electrolyte with the concentration of 0.002 mol/L;
(2) 5mg of block black phosphorus (purchased from Muscow Nana, purity > 99.999%) is placed on a tetrafluoro platinum sheet electrode clamp, is connected with a negative electrode of a direct current power supply and is used as an electrochemical cathode, Pt is used as an electrochemical anode, the two electrodes are kept in parallel, and the distance between the electrodes is 2 cm;
(3) immersing the block black phosphorus and Pt in the step (2) into the electrolyte in the step (1);
(4) applying 15V direct current voltage to the electrochemical system, and obtaining black phosphorus nanosheet dispersion liquid after 30 min;
(5) to the dispersion obtained in step (4), 0.002mol/L of gold acetate ((CH)3COO)3Au) and 0.0005mol/L reducing agent (ethylene glycol) are stirred for 1 hour to obtain the passivated black phosphorus nanosheet dispersion liquid.
Comparative example 2
The comparative example provides a passivation method of black phosphorus nanosheets, which specifically comprises the following steps:
(1) 6mg of tetrabutylammonium acetate (CH) are metered in by an electronic balance3COO.TBA), adding the mixture into a glass beaker containing 10mL of organic solvent DMF, and oscillating the glass beaker in an ultrasonic cleaner for 1min to obtain electrolyte with the gold particle concentration of 0.002 mol/L;
(2) 5mg of block black phosphorus (purchased from Muscow Nana, purity > 99.999%) is placed on a tetrafluoro platinum sheet electrode clamp, is connected with a negative electrode of a direct current power supply and is used as an electrochemical cathode, Pt is used as an electrochemical anode, the two electrodes are kept in parallel, and the distance between the electrodes is 2 cm;
(3) immersing the block black phosphorus and Pt in the step (2) into the electrolyte in the step (1);
(4) applying 15V direct current voltage to the electrochemical system, stopping applying the voltage after 30min, and adding 0.002mol/L gold acetate to obtain black phosphorus nanosheet dispersion liquid;
(5) dropwise injecting the black phosphorus nanosheet dispersion liquid obtained in the step (4) onto the liquid level of ultrapure water through a liquid transfer gun, and then using SiO2The Si substrate penetrates through the sections of the black phosphorus nanosheets and the water to obtain the black phosphorus nanosheets dispersed on the substrate;
(6) putting the black phosphorus nanosheets dispersed on the substrate into a CVD furnace, heating to 300 ℃, and introducing 100sccm H2And (4) carrying out hydrogen reduction to obtain the passivated black phosphorus nanosheet.
Test example 1
The following performance tests were performed on the black phosphorus nanosheet dispersion obtained in example 1:
standing the black phosphorus nanosheet dispersion liquid obtained in the step (4) in the example 1 for 0.5h to deposit a thick layer of black phosphorus nanosheets, and preparing a sample by using the upper layer of dispersion liquid, namely transferring the black phosphorus nanosheets in the upper layer of dispersion liquid to 300nm SiO2on/Si, the following tests were carried out on the prepared samples:
(ii) Raman Spectroscopy test
Testing an instrument: the model of a microscopic confocal laser Raman spectrometer of Raniesha company In England is Invia Reflex, and the test conditions are as follows: the excitation wavelength was 514nm at room temperature.
FIG. 2a shows the black phosphorus nanoplate protected by gold nanoparticles obtained in example 1 and the black phosphorus nanoplate not protected by gold nanoparticlesRaman spectrum contrast diagram of passivated black phosphorus nanosheet, the black phosphorus nanosheets protected by gold nanoparticles are 360.8cm respectively-1，438.0cm-1And 466.8cm-1Obvious Raman characteristic peaks are observed and respectively correspond to A of the black phosphorus crystal1 g，A2gAnd A2 gVibration mode, indicating that the flakes in the dispersion obtained in example 1 were still black phosphorus crystals; the same sample was then tested for Raman spectra at different days, and it can be observed from the test result of FIG. 2b that the sample still shows three characteristic peaks of black phosphorus after 30 days, and Ag 1/Ag 2Greater than 0.4.
Characterization by AFM atomic force microscope
Testing an instrument: an atomic force microscope of Bruker company, the model number of which is Dimension ICON, and the test conditions are as follows: room temperature, smart mode.
3a, 3b, 3c and 3d are characterization diagrams of AFM Atomic Force Microscope (AFM) of the black phosphorus nanosheets obtained in example 1, which are placed in the air for different periods of time, and it can be seen that the thickness of the black phosphorus is 3.2nm, and the black phosphorus nanosheets protected by the metal nanoclusters are not oxidized at all in the shooting process for 45 days;
characterization of optical microscope
Testing an instrument: an optical microscope of Shanghai Chuikang optical instrument Limited, the model is 9XB-PC, and the test conditions are as follows: and (4) room temperature.
Fig. 4a, 4b, 4c and 4d are optical photographs of the black phosphorus nanosheet obtained in example 1, which is placed in the air for different periods of time, and it can be seen that the lateral dimension of the black phosphorus nanosheet protected by the gold nanoparticles is 55 μm, and the black phosphorus nanosheet is not oxidized any more after 45 days of continuous shooting.
Photoelectric performance test
Testing an instrument: test source table (KEITHLEY 2614B) and laser signal generator (RIGOL DG1022), test conditions: and (4) room temperature.
FIGS. 5a and 5b are photoelectric data images of the black phosphorus nanosheets obtained in example 1, and the source-drain current I of the black phosphorus nanosheets can be seen from FIG. 5adsWith source drain bias voltage VdsIs increased byThe linear growth mode, indicating that the device operates in the linear region under this test parameter, indicates good ohmic contact characteristics without significant additional resistance at the interface. And the measured bias current is the largest when the gate voltage is-60V, and the measured bias current is the smallest when the gate voltage is 60V as the gate voltage is changed from-60V to 60V. According to the output characteristic curve relation of a typical P-type semiconductor. FIG. 5b shows that under excitation of visible light to mid-infrared laser, the black phosphorus nanosheets all have obvious photoelectric response.
Test example 2:
respectively standing the black phosphorus nanosheet dispersion liquid obtained in the examples 1-17 and the comparative examples 1-2 for 0.5h, taking the upper layer liquid of the dispersion liquid to prepare a sample after the thick layer black phosphorus nanosheet is deposited, and transferring the black phosphorus nanosheet in the black phosphorus dispersion liquid to 300nm SiO2on/Si, the following performance tests were carried out:
storage time of the black phosphorus nanosheet: shooting the black phosphorus nanosheets in the above embodiments for different days under an optical microscope respectively, and observing the storage time of the few-layer black phosphorus in different embodiments; the days of change in black phosphorus nanoplates were recorded. (oxidation is generated when small bubbles are generated on the surface of the black phosphorus nanosheet)
The test results are shown in table 1:
TABLE 1
| Black phosphorus nanosheet | Days of storage | Black phosphorus nanosheet | 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 can be seen from Table 1, the black phosphorus nanosheet obtained by the passivation method provided by the invention has excellent oxidation resistance, and can be stored in an air environment for a long time, wherein the storage time is more than 5 days, basically more than 15 days and maximally up to 45 days.
Comparative example 1 reduction with a chemical reducing agent destroys black phosphorus to some extent, which causes many holes on the surface of black phosphorus nanosheet, affects the performance of the black phosphorus nanosheet, and reduces the oxidation resistance. Comparative example 2 reduction was carried out by heating at a high temperature and introducing hydrogen gas, and the passivation effect was inferior to that of the example.
As can be seen from comparative examples 1 to 3, the protective effects on the black phosphorus nanosheets are greatly different depending on the types of metal ions doped in the electrolyte, and the protective effects are the best when the metal nanoclusters are gold (example 1), copper (example 2) and silver (example 3), and among them, the protective effect on the gold nanoclusters is the best.
As can be seen from comparative examples 1 and 4 to 9, the higher the concentration of the metal ions, the more the obtained metal nanoclusters are, the better the protection effect on the black phosphorus nanosheets is, but when the concentration of the metal ions is too high, the exfoliation of the black phosphorus nanosheets is affected, and the obtained black phosphorus nanosheets are low in yield, small in size and thick in thickness, preferably the concentration is 0.001 to 0.006mol/L, more preferably 0.002 to 0.006mol/L, and most preferably 0.002 mol/L.
It is understood from comparative examples 1 and 10 to 12 that the longer the peeling time, the more metal nanoclusters obtained by electrochemical reduction, and the better the effect of protecting the black phosphorus nanosheet.
It can be seen from comparison of examples 1 and 13-17 that the higher the voltage, the faster and more the reduced metal ions, the better the protection effect; however, when the voltage is too large, the stripping of the black phosphorus nanosheet is influenced, the obtained black phosphorus nanosheet is small in size and thick, the storage time is not prolonged any more, and the energy waste is caused, and the preferred voltage is 10-25V.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A passivation method of black phosphorus nanosheets, the passivation method comprising the steps of:
immersing the anode and the cathode into electrolyte containing tetrabutyl cations and metal ions, and applying direct-current voltage to obtain passivated black phosphorus nanosheet dispersion liquid;
the cathode includes black phosphorus.
2. The passivation method according to claim 1, characterized in that the metal ions comprise any one or a combination of at least two of copper ions, silver ions, platinum ions or gold ions, preferably gold ions;
preferably, the molar concentration of the metal ions in the electrolyte is 0.0005 to 0.01mol/L, preferably 0.001 to 0.006mol/L, and more preferably 0.002 mol/L.
3. Passivation method according to claim 1 or 2, characterized in that the tetrabutyl cations comprise tetrabutylammonium ions;
preferably, the tetrabutyl cation is derived from tetrabutyl quaternary ammonium salt;
preferably, the tetrabutyl quaternary ammonium salt comprises any one or at least two of tetrabutylammonium acetate, tetrabutylammonium chloride and tetrabutylammonium phosphate, preferably tetrabutylammonium acetate and/or tetrabutylammonium phosphate, preferably tetrabutylammonium acetate.
4. A passivation method according to any one of claims 1-3, characterized in that the black phosphorus is bulk black phosphorus;
preferably, the dosage of the black phosphorus in the cathode is 5-10 mg;
preferably, the anode comprises a Pt foil.
5. Passivation method according to any one of the claims 1-4, characterized in that 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, preferably N, N-dimethylformamide.
6. Passivation method according to any one of the claims 1-5, characterized in that the direct voltage is 7-25V, preferably 10-25V, further preferably 15V;
preferably, the time for applying the direct current voltage is 10-40min, preferably 30 min.
7. The passivation method according to any one of claims 1 to 6, further comprising: after the application of the direct-current voltage, standing;
preferably, the standing time is 0.1-1h, preferably 15 min;
preferably, the passivation method further comprises: dropwise adding the passivated black phosphorus nanosheet dispersion liquid onto the liquid level of ultrapure water, and then penetrating the sections of the passivated black phosphorus nanosheets and water by using a substrate to obtain black phosphorus nanosheets dispersed on the substrate;
preferably, the passivated black phosphorus nanosheet dispersion is injected drop-wise onto the surface of ultrapure water by a pipette.
8. Passivated black phosphorus nanoplates obtained by the passivation process of any one of claims 1 to 7.
9. Passivated black phosphorus nanoplatelets according to claim 8 wherein the number of layers of said passivated black phosphorus nanoplatelets is 10 or less, preferably 8 or less;
preferably, the thickness of the passivated black phosphorus nanosheet is 2-7nm, preferably 2-4 nm;
preferably, the transverse size of the passivated black phosphorus nanosheet is greater than or equal to 10 microns, preferably 10-100 microns;
preferably, the days of the storage of the passivated black phosphorus nanosheets in the air are more than or equal to 15 days, preferably more than or equal to 30 days, and further preferably more than or equal to 45 days.
10. Use of the passivated black phosphorus nanoplates of claims 8 or 9 in the preparation of semiconductor integrated photovoltaic devices, in the preparation of optical films, in the preparation of gas sensors, in the preparation of biosensors, in the preparation of solar cells, or in electronic printing.
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